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Preface

w r : ~ T qar:
T I"
(All that exists was born from the Sun)
-Brhad-devata, I: 61

In the last ten years photochemistry has seen a tremendous upsurge of
interest and activity. A great deal of fundamental knowledge about the
excited states has come to light as a result of the advent of tunable and
high intensity laser beams. The field is developing so fast that any know-
ledge gained becomes outdated before it is fully comprehended. In the
circumstances, perhaps another textbook is justified.
This book is written as a university level textbook, suitable for graduate,
postgraduate and research students in the field of photochemistry, photo-
physics and photobiology. During the long years of teaching photo-
chemistry a t the graduate and postgraduate levels, I have always found it
difficult to recommend a single textbook to the students. My first
introduction to photochenlistry was through Bowen's Chemical Aspects of
Light which very lucidly explained the interactions between radiation and
matter and their consequences and which has influenced me the most
although photochemistry has travelled a long way since then. I have
freely taken the help of books and monographs which are now available
on the subject. All these books are listed in the beginning of the biblio-
graphy. J.B. Birks' Photophysics of Aromatic Molecules, N.J. Turro's
Molecular Photochemistry, J.P. Simons' Photochemistry and Spectroscopy
and A.A. Lamola and N.J. Turro (ed) Organic Photochemistry and Energy
Transfer are some of the books from which I have drawn heavily. To these
should be added the many review articles which have been of great help.
I have adapted diagrams from son-. of these articles which have been
acknowledged.
As the title implies, the book emphasizes the fundamental aspects of
photochemistry. The first section introduces the subject by enumerating
the relevance of photochemistry. Since the vocabulary of photochemistry
is that of spectroscopy, the second section in which is discussed energy
level schemes and symmetry properties, is like a refresher course. In the
third section the actual mechanism of light absorption is taken up in
detail because the probability of absorption forms the basis of photo-
chemistry. A proper understanding of the process is essential before one
can appreciate photochemistry. The next three sections present the

X PREFACE

propertics of the electronically excited states and the fundamentals of
photophysical processes. The primary photochemical processes form a
separate section because chemical reactions in the excited states present
certain new concepts. The rest of the book is mainly concerned with the
application of the knowledge so gained to some typical photochemical
reactions. Some current topics which are being actively pursued and are
of great relevance have been presented in section nine. The last section
Contents
discusses the htest tools and techniques for the determination of various
photophysical and photochemical parameters. An attempt has been made,
as far as possible, to explain the concepts by simple examples. A summary
is given at thc end of each of the Erst six sections which deal mainly with the
fundamental aspects.
My thanks are due to tlie University Grants Commission for approving
the project for writing this book and for providing necessary funds and
facilities, and to the National Book Trust for subsidizing the book. I
take this opportunity to acknowledge with thanks the help and suggestions
that I have received from various quarters. I am deeply indebted to my
teacher Dr. E.J. Bowen, FRS, Oxford University, for going through the
entire manuscript with a 'fine-toothed comb' as he puts it, for suggestions
and criticisms and for writing a Foreword to this book. Only because
of his encouragement could I confidently embark upon a project of such
magnitude. I also thank professors C.N.R. Rao, M.R. Padhye and
H.J. Arnikar for their valuable comments. Mention must be made of
S.K. Chakraborty, A.K. Gupta, P.K. Bhattacharya, S.K. Ash, U. Samanta,
S. Basu and Shyamsree Gupta, who have helped me in various ways. To 1. Introducing Photochemistry
the scholar-poet professor P. La1 I owe a special debt for suggesting a 1.1 Importance of photochemistry
beautiful couplet from the Vedas, pronouncing the glory of the Sun-the 1.2 Laws of photochemistry
soul df the world. 1.3 Photochemistry and spectroscopy
Words fail to express the patience with which my husband, Dr. S.K. 1.4 Units and dimensions
Mukherjee bore my writing bouts at the cost of my household duties. His
1.5 Thermal emission and photoluminescence
constant encouragement gave me the moral and mental support which I
needed in large measure in course of this arduous task.
A new chapter has- been added in which the case history of a photo-
chemical reaction has been taken up from preliminary observation to 2. Nature of Light and Nature of Matter
considerable sophistication. The purpose behind this exercise was to intro-
2.1 Interaction between light and matter
duce the students to the methodology for the mechanistic study of a
2.2 Wave nature of radiation
photochemical reaction. 2.3 Particle nature of radiation
2.4 Dual nature of matter
2.5 Electronic energy states of atoms
Calcutta K.K. ROHATGI-MUKHERJEE 2.6 The selection rule
2.7 Diatomic and polyatomic molecules
2.8 Spectroscopic terms for electronic states
2.9 Orbital symmetry and molecular symmetry
2.10 Notation for excited states of organic molecules
2.11 Energy levels for inorganic complexes

1 Types of photophysical pathways 126 9.8 Excited state acidity constants-pK* values 106 4. 7 The rules governing the transition between two 6 .6 Emission property and the electronic configuration 5.10 The effect of temperature on emission processes 3. vibrational and rotational energies 91 4. 3 Effect of light intensity on the rate of photochemical 4. 2 Radiationless transition-internal conversion and 9.5 Solar energy conversion and storage .8 Directional nature of light absorption 6 .3 Time-dependent Schrodinger equation 3 . Physical Properties of the Electronically Excited Molecules 4. 4 Fluorescence and structure 140 9. 2 Bimolecular collisions in gases and vapours and the energy states mechanism of fluorescence quenching 3. 2 Einstein's treatment of absorption and emission 5. 4 Kinetics of collisional quenching: Stern-Volmer molecules equation 3.1 Photoreduction and related reactions 4.5 Concentration dependence of quenching and excimer 3. Photophysical Kinetics of Bimolecular Processes 3 .12 Wigner's spin conservation rule 122 8. 5.4 Shapes of absorption band and Franck-Condon 7 . 1 Electric dipole transitions 5. 6 Quenching by foreign substances 4.9 Excited state redox potential 111 8.6 Transition metal complexes 5. Some Aspects of Organic and Inorganic Photochemistry 4. 3 Collisions in solution 3.5 Triplet states and phosphorescence emission of Photochemical Interest 5.11 Two-photon absorption spectroscopy formation 6 .3 Cycloaddition reactions 4. Mechanism of Absorption and Emission of Radiation 5.10 Emission of polarized luminescence 113 8.10 Types of electronic transitions in organic molecules 6.8 State diagrams 3 . 6 Intensity of electronic transitions 6.2 Electronic.6 Environmental effect on absorption and emission 7 .9 Life times of excited'electronic states of atoms and 6 . 1 Classification of photochemical reactions 4.1 Nature of changes on electronic excitation 90 7.7 Excited state dipole moment 103 8. Some Current Topics in Photochemistry 5.13 Study of excited states by Rash photolysis experiments 8. 2 Rate constants and lifetimes of reactive energy states principle 94 7 .5 Emission spectra 99 reactions 4. 4 Types of photochemical reactions spectra 101 4. Photophysical Processes in Electronically Excited Molecules 9.2 Photooxidation and photooxygenation 4.3 Potential energy diagram 92 7 .9 Delayed fluorescence phenomena 5.1 Kinetic collisions and optical collision 3 .1 Origin of life 5 .4 ~hotoelectrochemih of excited state redox reaction 5 .7 Photophysical kinetics of unimolecular processes 3 .4 Woodward-Hoffman rule of electrocyclic reactions 4. Photochemical Primary Processes 4. xiii xii CONTENTS 3.3 Photosynthesis .11 Geometry of some electronically excited molecules 121 8.2 Mutagenic effect of radiation intersystem crossing 129 9.3 Fluorescence emission 137 9. 4 Time-dependent perturbation theory 3.5 Chemiluminescence and laser beams 123 8.5 Correlation with experimental quantities 6 .

is a rapidly developing subject and helps the understanding of phenomena like photosynthesis. Synthetic organic photochemistry has pro- vided methods for the manufacture of many chemicals which could not .1 Light sources and their standardization 10. Tools and Techniques 10. In the primitive earth conditions radiation from the sun was the' only source of energy.7 Photoreactive state of anthracene 11. chemistry and biology. The relevance of photochemistry also lies in its varied applications in science and technology. the origin of life itself must have been a photochemical act. the photochemistry of biological reactions. ONE chemical reactions 10. Case History of a Photochemical Reaction 11. 11.4 Lasers in photochemical kinetics 11.3 Mechanistic deductions from the experimental observations on photoreaction 11.2 Measurement of emission characteristics: fluorescence. photodynamic action. In doing so it tries to integrate knowledge of physics. Simple gaseous molecules like Index methane.6 Fluorescence quenching of anthracene by CCI. nature has perfected her machinery for the utilization of solar radiant energy for all pbotobiological phenomena and providing food for the propagation of life itself. Photochemistry is basic to the world we live in.5 Reactivity of carbon tetrachloride with substituted anthracenes 11.4 Reaction of anthracene with other halogenated solvents 11. Through the ages.2 Determination of quantum yields of reaction 11. With Bibliography sun as the central figure. vision and mutagenic effects of light. phototaxis. Such molecules are produced by the quantum yields absorption of suitable radiation in the visible and near ultraviolet region of the spectrum. phosphorescence and chemiluminescence 10. CONTENTS 10.3 Techniques for study of transient species in photo.1 IMPORTANCE OF PHOTOCHEMISTRY two plane polarized radiation Appendix 11: Low temperature glasses Photochemistry is concerned with reactions which are initiated by Appendix IU: photokinetic scheme for determination of electronically excited molecules.1 Photochemical reaction between anthracene and Introducing carbon tetrachloride Photochemistry 11.8 Mechanism of photoperoxidation Appendix I: Mathematical equation for the combination of 1. photo- periodism. ammonia and carbon dioxide must have reacted photochemically to synthesize complex organic molecules like proteins and nucleic acids. Photobiology.

for detection of cracks in metal work. These are known as photochromic observed and studied qualitatively. as luminescent dials for watches. The deleterious effect of sunlight on coloured cotton are discovered and devices for proper utilization of this abundant source fabrics is of everyday experience. These are known as energy degraders o r led to the proper understanding of chemical reactions.. But they have found application in nineteenth century. transfer and the intricate structure of matter. The Beer law states that the amount of radiation found wide fields of application. Some examples of diamonds.. green light for reading Only that light which is absorbed by a system can cause chemical chnnge. Researches various photophysical and photochemical processes is essential. photosynthesis in plants. (iv) manufacture of provided by the energy crisis. as 'optical brighteners' in white cally substituted compounds by using appropriate beams from tunable dress materials. Moreover. a s paints in advertisement hoardings which show enhanced dye lasers. A well known example is the spiropyrans. blackening of silver halides. If suitable photochemical reactions electronic industry. The quantitative approach to photo- chemistry was initiated by Grotthus and Draper in the beginning of the materials. The light absorbed by dyes used for colouring the fabric initiates oxidative Solar batteries working on the principle of photovoltaic cffects is one chain reaction in cellulose fibres. modes of energy photostabilizers. as microanalytical re~gents. it and blue light for erasing it. tion to a tiny point is used for eye surgery. and many such industrially viable photochemical syntheses may be mentioned here: The zdvent of tunable dye lasers has increased the possibility (i) synthesis of vitamin D. etc. that is. (iii) industrial A further impetus to the study of photochemical reaction has been synthesis of caprolactam. In these areas. photochemistr~~. Solar energy provides a readily available source of energy. o-hydroxybenzophenones. their absorption Prior to 18 17. the daily incident energy per square kilometre photography. from ergosterol isolated from certain of their application in science and technology. such device. and expressed as The intense and powerful beam of coherent radiation capable of concentra- . of energy perfected. brilliance by utilizing fluorescence. lithoprinting and manufacture of printed circuits for the is equivalent to 3000 tonnes of coal. when exposed to suitable radiation and reverse when the irradiation source is removed. The two are combined second processes of nonradiative decay of excitational energy in molecules. Law. half the world's energy problem might be solved. Lasers are intense sources of monochromatic and that each sgccessive layer of the medium absorbs an equal fraction of and coherent radiation. the understanding of Similar depolymerizing action is observed in plastic materials.g. For basic researches in these fields. boring vity of these methods have an added advantage. by photosulphonation. processes which plants carry out intermediates) by photochlorination. as military range finders and detectors. insecticides and halogenated aromatics (used as synthetic conversion and storage of solar energy. cutting metals. The Lambert law states that the fraction of incident radiation absorbed Another revolutionary application of electronically excited molecular by a transparent medium is independent of tile intensity of incident radiation systems is in laser technology. was characteristics. Certain chemicals change their colour. It was realized that all the incident light was not effective in bringing about a chemical change and the jrst law of information storage and self-developing self-erasing films in digital com.2 FUNDAMENTALS OF PHOTOCHEMISTRY INTRODUCING PHOTOCtIEMISTRY 3 be produced by dark reactions. for tracing the course of river through caves. Now it is possible to excite individual vibronic levels or isotopi- screens. X-ray and TV states. greater efficiency and selecti. the study of diverse phenomena ranging from moonquakes to pico. 1. From their early development in 1960 they have incident radiation. and (v) synthesis of antioxidants so efficiently. now known as Grotthus-Draper law was formulated: puters also. the monomer for Nylon 6. It is said that a company experimenting on such photochromic memory used UV light for writing the information. This has initiated researches into the cleaning solvents. photochemical changes such as photofading of coloured materials. the worst sufferers being window curtains. that is the concer:tration C of the absorbing species. They have provided powerful tools for absorbed is proportio~~aZ to the w m b e r of molecules absorbing tlze radiat~e. (ii) synthesis of cubanes which are antiviral agents. The are going on t o find suitable colourless chemicals which when added t o fundamental study of excited states of molecules is exciting by itself. Their use in photochromic sunglasses is obvious.2 LAWS OF PHOTOCHEMISTRY and so on. Unfortunately organic substances usually The probability or rate of absorption is given by the Lambert-Beer lack the stability for very large numbers of reversals. e. Flash photolysis and The photophysical phenomena of fluorescence and phosphorescence pulsed laser photolysis are newer tools for the study of higher energy have found varied applications in fluorescent tube lights. dyed materials or plastics will take over the excitation energy and divert Short-lived energy states with nano and pico-second reaction kinetics have it to nondestructive pathways. especially in those countries which lie between the tropics of cancer and Photoinitiated polymerization and photopolymerization are used in capricorn. This causes the tendering of cotton.

Excited molecules may uhere e. I=optical provides a mode of account-keeping for partition of absorbed quanta into path length. we get The second law of photochemistry was first enunciated by Stark (1908) (i) I = I. and (ii) I = I.ollimating shield. ineasures the amount of solute per unit area of the layer. When high intensity light sources as from flash lamps or lasers are used 'biphotonic' photochemical effects may occur which modify the application of the Einstein law. = aV/2. At very high intensities a molecule may absorb two photons simultaneously. when I = 0. LS=light source.by the system is where a. I. Fzfilter. or alternatively may trigger off function of frequency v. The concept of quantum yield can be beam of radiation of cross-seciional area A. Work by Warburg and Bodenstein (1912-1925) clarified earlier confusions between photon absorption and observed chemical change. Since mole c=volume -.transmitted light various pathways. i where evt is the molar absorptivity at frequency VI for the ith component whose concentration is CI. a morecommon effect. C=reaction cell. the concentration is expressed in moles per litre thermal reactions of large chemical yield. The socalled 'law'. I ) . is for a second photon of longer wavelength to be absorbed by a metastable (triplet or radical) species produced by the action of the first photon. transmitted illtensity respectively (Figure 1 . dl being the thickness of the layer. The S1 units of c. when 2 = 1. ci. The final form is expressed in the decadic logarithm. quantum yields as observed vary from a million to a very small fraction of unity..1) within the boundary conditions. however.4) 4reaetlon = number of quanta absorbed (1. is the proportionality constant. 10-incident light jntensity..303. the quantity commonly known as the optical density OD or absorbance A . lo and I are thc incident and about the primary photochemical act. assuming path length to be unity. extended to any act.1 Optical arrangenle~~tfor a photochemical reaction by a collimated dependent on the light intensity. physical or chemical.l respectively. intensity. A plot of quantum eficiency is defined as ev (or its logarithm) vs wavelength or wavenumher gives rise to familiar absorption bands. The quantity Cdl. The nature of the photo-products and the quantumyields are here Figure I . S=c. Hence the mole measured OD is Therefore. following light absorption. Since number of molecules decomposed or formed I = lo10-~vC1 (1. The quantity log loll is To express the efficiency of a photochemical reaction. therefore. The Stark-Einstein law states that: One quantum of light is absorbed per molecule of absorbing and reacting substance that disappears. _ mole area x thickness For more than one absorbing components. . Molecules log '" = €" Cl which absorb photons become physically 'excited'. It L=lem. is called the rrtolur extincrion cocficient and is a lose their energy in nonchemical ways. we have and later by Einstein (1912). r t z and n ~ h o l .7) The concept of quantum yield or quantum efficiency was first introduced by Einstein. optical density is ZevdCII. INTRODUCING PHOTOCHBMISTRY 5 4 FUNDAMENTALS OF PHOTOCHEMISTRY the amount of light absorbed lo. Because of the frequent complexity of photo- reactions. Cdl = - area On integrating equation (1. I and 6 are nzol rarely holds in its strict sense. but rather provides essential information d 1 r 3 . and 1 is the optical path length in cm. and this must be I distinguished from becoming chemically 'active'. known as absorption coefficient: is a function of frequency or wave- length of radiation.

..00 x 108 m s-I. Quantum mechanics has played a vital part in descrihirlg the velocity of light energy states of molecules. the energy equivalent of a photon of this wavelength is calculated as E. All the other units are derived from these fundamental units. The propor- E. Planck's constant photoexcited molecule. From Bohr's relationship. of wavelength 365 nm. energy is required in two ways: (i) as energy the wavelength of radiation h is expressed in nanometres (1 nm = lo-@m).186 J).E = hv Rate of absorption is expressed in einstein per unit area per second (1. first excited electronic state \+ill be The bond dissociation energy per mole for most of the molecules lie = 5. l . c = 3. the energy barrier is bypassed due to energy absorbed to promote one mole of anthracene molecules to the electronic excitation and one of the products may appear in the excited state. The iinit 1. The enthalpy of reaction is the net heat change associated with the breaking and making of bonds leading to reaction products. The Therefore in the SI units: need for energy of activation arises because on close approach.. cm-'. to upper energy state E. This signifies that a photon of this wavelength is absorbed by the in nm) can be calculated from the simplified expression anthracene molecule to promote i t from the ground energy state El. photochemistry and spectroscopy are intimately h = 6.44 x 10-'9 J photon-' x 6. In photochemical reactions. For example.27 x lo5 J mol-I number of photons of wavelcngthr lying between 800 nm and 200 nm respectively. In This quantum of energy is contained in a photon of wavelength 365 nm.g) where.62 x J S..10) tionality constant hc. which correspond to the visible and near ultraviolet regions of = 327 kJ (ki!ojoule) mol-l the electromagnetic spectrum. = E. related. When expressed in wavenumber in reciprocal centimetre (cm-l) or wave- length in nanometre (nm) and substituting the values for h and c (the The energy of radiation is quite often expressed In terms of kilo- velocity of light). In this system. and (ii) as enthalpy or heat of reaction AH. (1 calorie = 4. Thus.02 x loz3photon mol-1 between 150 k J and 600 kJ: These energies are available from Avogadro's = 3. the charge clouds of the two reacting partners repel each other. For any chemical reaction. caloric. is replaced by joule ( 1 J = 1G7 erg) to rationalize Since the primary photoprocess is absorption of a photon to create a the definition of thermal energy. measurable quantities are expressed in SI (System Internationalk) units and replace the centjmetre- . INTRODUCING PHOTOCHEMISTRY 7 FUNDAMENTALS OF PHOTOCHEMISTRY 1 . thermal or dark reactions.3 PHOTOCHEMISTRY AND SPECTROSCOPY of thermal energy.rate of the process gram-second (cgs) system. anthracene has an absorption band with a maximum at wavelength The energy of a n einstein of radiation of wavelength A (expressed 365 nm. The same range of energies is required This amount of energy is contained in one mole or one einstein of photons for electronic transitions in most atoms and molecules.. the unit of wavenumber is used to express energy.. Sometimes. we get calorie per mole (kcal/mole). . 4 UNITS AND DIMENSIONS number of molecules undergoing that process 4 ~ I 0 ~ 8 8= 8 number of quanta absorbed Ac:ording to the modern convention. merely . Some values for the energy of radiation in the visible and ultraviolet regions are given in Table 1 . The reactants must have sufficient energy to overcome this energy barrier for fruitful inber- action.= h v = h c v (v = C V ) (1. the energy of activation is supplied as heat An Avogadro number of photons is called an cinstrin. 5. The amount of energy. the unit of length is a metre rate of absorption (m).44 x erg photon-I . is implied therein. A chemical potential of one volt signifies an energy of one electron volt per molecule. the unit of mass is kilogram (kg) and the unit of time is second (s). h = Planck's constant and v is the frequency of absorbed radiation. The unit of electron-volt (eV) is used for single atom or molecule events. . of activation AE.

wave..cm-l= m v a= 5.222 conditions. under steady state Violet 450 22.03 x loz4 x A (nm) x power (watt) hcu einstein . We have.8. Hence . Yellow 590 16.992 x 10-24 J m-I' C2= 1 .000 Ultraviolet they also emit some of these frequencies.watt . intensity I can be expressed in number of quanta m-2 s-l.15) by c/4 where c is the velocity Power = -. .000 Green environment rates of absorption and emission are equal (Kirchhoff's law). expressed in different units Approx.5 THERMAL EMISSION AND PHOTOLUMWESCENCE Region length range Wavenumber kJ kcal nm cm-1 Atoms and molecules absorb only specific frequencies of radiation dictated by their electronic configurations. 620 16.129 Red The total energy E.e. emits all frequencies with unit efficiency. the expression for energy density can be converted into energy m2 m2 s flux E.06 kcal mol-I = 96.949 Molecules electronically excited by light are not in thermal equilibrium Orange with their neighbours.37 x 1016quanta s-l m-P or 1 .000 as one wbich absorbs all the radiation falling on it and. Such an absorber Blue is called a black body.0135 kJ mol-l 1 eV mol-l= 23.5. = - .333 black body at temperature T K is given by the Stefan-Boltzmann law E=aT4 (1.1 If the area of the reaction vessel exposed to the radiation is A.186 J From Planck's radiation law.544 This equilibrium is disturbed if energy from another source flows in. 570 17.14) c 1 where the Stefan's constant A (nm) =. A perfect absorber is defined 400 25.36 x h (nm) x power (watt) Also I= m2 s For example. that is = 0. Since The corresponding radiation density within frequency range v and power is energy per unit time and each photon has energy associated with + v clv is it.39 kJ mol-l where Cl = 4. fiJTRODUClNG PHOTOCHEMISTRY 9 8 FUNDAMENTALS OF PHOTOCHEMISTRY TABLE 1.439 x 10% m deg and k = Boltz- The intensity of incident flux from light sources is in general defined mann constant = 1 . Energy mol-1 eV 1. i. a helium-argon laser with a power of 2 x W at 632 8 nnl will emit 6.66x einstein s-l m-z. in terms of power.J On multiplying the expression (1 .859 cal mol-I px dA.699 x lo-* J m-2 deg-4 s-I 1 cal=4. . E = nhic and watt . the energy per m3 of radiation or raaia- 1 eV = 1. Under suitable conditions 200 50. of all wavelengths radiated per m2 per second by a 750 13. the energy emitted in units of J per second per unit area within unit wavelength interval at wavelength A (expressed in nm) by an ideal black body of surface area A at T K .38 x J molecule-l.6 x 10-l0 J + tion density p in an enclosuie having wavelength between A and A dh is 1 cm-I mol-l = 2. of light. watt per unit cross-section (watt = J s-I). When a system is in thermal equilibrium with its 500 20. the rate of Energy of electromagnetic photon in the visible and uv regions incidence is gilen as the intensity I times the area A.

In the integrated form I.~lacld applietl sciences. obtained by dividing by c/4. It is characteristic of the absorbing system. Photozlwmiitry and spectroscopy are related intimately.~ Planck's equation is divided 4. 3.<=av I Cdl )vIrcrr av I S the prnportio~~fl/i/y co~zstant. For low temperatures and frequencies in the optical range ef~vl" > 1 the following simplification can be made: Ligh: emitted from a black body solely as a result of high temperature as in electric bulb is known as incanclesccncc or therrnal radiation. defined as + = -number of molecules - decomposed o r formed per unit number of quanta absorbed per unit timc .10 FUNDAMENTALS OF PHOTOCHEMISTRY INTRODUCING PHOTOCHEMISTRY 11 To express in units of quanta n ~ s-l. 2 The first law of photochemistry states: Only fhnt l i ~ h twhich r c irhtorhrd b ) ~o ryytcm cart r n i i ~ rclietrl~ralchn11:70 (Grotthus-Draper Law).sn/~/)~wr. Quality and quantity of photoluminescence is charactel.istic of the absorbing Planck's equation applies strictly to the emission into space at absolute system.c ab~orhitlesystrrn .i basically functions of temperature.hf is obsorbctl /I(. log I =cv CI-optical density where av=av!7.. 1 ~ : Frnrtio~lnl liqht nbsorptiorz is proportional to conrentrotton C ~ r imrlll-1 arlii the thichnrss dl of t11.acrirzg substaricrs that di. Summary 1. T =.. . but for wavelengths in the visible and ~lltraviolet region from incandescent sources. The rate of emission per unit area per unit wavenumber interval is 7. .- time --- where Qv is quantum density per unit frequency interval per second. (where h is Wien's constant = 2 898 x m (kg). 6.rnol~~cril~~ of by the energy o f one quantum Izv: ahsorbing atid rc. YAot~luminesccnc~ is known as cclrl light. this is substantially the same as emission into space at room temperature... A. as in fluorescent tube lar-nps.303 is called the molar extinction coefficient and is a function of frequency or wavelength. 8. On the other lraud. Quality and quantity of thermal emission is n function of temperature only. h. are 11c. Photochemistry has made large contributions to the fundarnent. The probability o r rate of absorption is given by I nmbert-Beer 1 . The wavelength of most strongly emitted radiation in the contl- nuous spectrum from black body is given by Wien's Displacement L ~ W . The second law states: Orle q u a ~ ~ t uomf li. rero. The efficiency of a photochemical reaction is expressed in terms of a quantity called quanttim yield +. 5. Tllc quality and quantity of thermal radiation is a function of temperature only. the quality and quantity of emission from :!TI electronically escited molecule.

and to understand light we must involve matter. because to understand matter we have to make use of light. and take the help of various types of spectro- scopic methods for the understanding of the intricate architecture of atoms and molecules (Figure 2. All light measuring devices are based on such interactions. transmits. Even our knowledge of the physical world is based on such interactions. A microscope will view a particle only when incident light is scattered by it into the aperture of the obje. A beam of light in a dark room will not be visible to us unless it is scattered by dust particles floating in the air. Here. basic understanding of the interaction of light with matter. we use X-rays to elucidate the structure of molecules in their crystalline state. scatters or absorbs it and thus allowing us to understand its behaviour. if we wish to study the nature of light. we must first . by light we mean the conlplete spectrum of the electromagnetic radiation (Figure 2. hence Iigbt and radiation have been used synonymously.1 INTERACTION BETWEEN LIGHT AND MATTER The interaction between light and matter is the basis of all life in this world. In some of these interactions light behaves as a particle and in some others its behaviour is akin to a wave motion.1) from radioactive rays to radio waves. to obtain .1). Therefore. For example.tive. we must let it fall on matter which reflects. TWO Nature of Light and Nature of Matter 2. On the other hand.

If the particle moves with a steady speed. is a vector constant in time and space. In Figure 2.2 the radiation is propagated along the x-direction with a velocity c m s-'. sin 2n ( vt . The other parameters which define the motion of the wave are : A = wavelength in nano~netres(1 nm = metres) v = frequency or number of oscillations per second in Hertz (I-Iz) A = amplitude of oscillation at any point x Amax = antinode c = h v = velocity in tn s-l (a constant) T = time period in s = I/v - . This field is generated by the acceleration or deceleration of charged particles which act as the source of radiation.re satisfied (see Appendix 1). as emitted from an incandescent body or any other source is norn~allycompletely depolarized. A plane polarized radiation oscillates only in one plane. By using suitable devices. = wavenumber in cm-I = I/h $I = phase = s l h 277 $ = 2% x/h = phase angle or the angle whose sine gi\ e b the djsplace- ment at any point. . the field due to the charge will follow the motion and the medium will be undisturbed. = E. indentilied with the amplitude of oscillation.- where E y is the electric field strength vector in y-direction. The plane containing the displacement vector is the plalze of polarization. and E. A combination of two wave trains polarized in different planes gives rise to linearly.14 FUNDAMENTALS OF PHOTOCHEMISTRY NAME OF LIGHT AND NATURE OF MATTER understand the nat~rreof radiation and the nature of matter. elliptically or circularly polarized radiations when certain phase relationships a. radiation plane polarized in any desired direction can be obtained. Radiation. The electric vector is directed along the displace~nent direction of the wave called the direction of polarization. I = intensity at any point x =square of displacenient at that point node = point where the amplitude is zero. A disturbance will be generated and propagated in space. But if there is acceleration the field will not be able to follow the change. 2. The variation of the field strength as a function of time and space is given by the expression E.2 WAVE IVAl URE OF RADIATION From Maxwell's theory of electromagr~etic rad~ation we know that light travels in space in the form of an oscillating electric field.

field strength is given as form a conjugate pair and A E A t -- h. A p becomes large and vice versa... + magnetic dipole Expressing p in terms of energy of the system 1 5x lo-= where figures represent the relative intensities. + Vz = Potential energy operator h2 explain the distribution of energy radiated from a black body in thermal Jf r .62 x Js).2) This principle has profound influence on our study of the structure of matter. 3 PARTICLE NATURE OF RADIATION rential equation which can be solved to obtain the total energy E of a A particle is defined by its mass m and its momentum p or energy E. Corresponding to each eigenfunction. En. E2. the rest mass of a photon is zero. where m is the mass of a photon and c is the velocity of light in vacuum. If A x wave. The idea that light travels as photons was originated by Einstein in 1905. Similarly. On solving 2 .. The necessity for where p is the magnetic permeability and e the dielectric constant of the such a probability distribution function immediately suggests the notion of medium in which the radiation is propagated. If Ax is made directed perpendicular to the electric vector. this principle implies that our potential field can have only definite energy values for its motion. there are the characteristic Our understanding of the basic nature of matter is limited by Heisen. Tn this equation Y is known as the eigenfuncrion and E the eigenvalur or the characteristic energy value corresponding to this function. .Laplacian operator (de1)2 dz2 - From the theory of relativity. where h is the Planck constant (6.8- x2m v2 + V = Hamiltonian operator h equilibrium with the surrounding. The variation of magnetic small.4) where or mc = hvlc = momentum of a photon ~2 d' z2 + dyda + - dS ... Bohr's concept of well defined orbits is invalidated and the The amplitudes of the two fields are related as only way to express the dynamics of electron motion in atoms is in terms EolEio= d q (2. A p is angles to itself as well as to the direction of propagation. and time t. The Schrodinger equation is a second order diffe- 2 . .16 FUNDAMENTALS OF PHOTOCHEMISTRY NATURE OF LIGHT A N D NATURE OF MATTER 17 An oscillating electric field. Hz = H. The electric dipole compo- nent is the most important component involved in the interaction between light and matter. The magnetic the inherent error in the measurement of its momentum such that the field oscillates in phase with the electric field and the magnetic vector is product A x A p -. generates a magnetic field H. Combining the two. Yr. .. . where E is the total energy and V is the potential energy. It is measurements of the position and momentum of a particle of subatomic governed by the condition that the motion shall be described by a standing mass arc always in error when radiation is used to study matter. Stated simply. 4 DUAL NATURE OF MATTER this equation. in the same experiment. energy E. The quantum concept was introduced by Max Planck in 1900 to V. energies E. sin 2x (vt . One quantum of radiation is called a photon. Yz.. E = mc2. de Broglie emphasized the magnetic field disturbances can be broken down into multipole components dual nature of matter and obtained an expression similar to that of the of the field : light wave in which de Broglie's wavelength h for the electron wave is related to the momentum p of the particle by Planck's constant h .xlh) (2.. Yn are obtained. . The energy of a photon is also given by Einstein's equation.+ V . at right is the error in the location of the particle. E. In 1924. An expression for describing such a wave motion was obtained by Schrodinger in 1925. a number of values for Y such as 'To. we obtain S Y = E Y (2 7) mc2 = hv (2. h where h is Planck's constant. dynamic system when expressed as a sum of kinetic and potential The particle nature of light is visualized in the form of a wave packet or a energies: quantum of radiation whose energy is given by the relation E = hv. Electric dipole + Electric quadrupole + . E. Thus an electron constrained to move in a berg's uncertainty principle. The electric and the a three dimensional standing wave.3) of probability distribution functions called orbitals.

1=0 @ = Y". (Figure 2.. m and s).. therefore. 3 are shown in Figure 2. & l.. 3 . the set of 1 values for a given n orbital have the functions.&)as p For the H-atom. Normally. m = 0. In the absence of the field. o8 (2. I.fold degenerate and can have Values 0.10) where Y is the space dependent function and a depends on the spin 1=0. such that the maximum value is excited He atom. 3 respectively. The magnetic momentum quantum numbers are eigenvalues of the operator izsuch that The pictorial representation of radial and spherical distribution functions for values of n = 1. It was introduced enlpirically by Uhlenbeck and Goudsmit system and is related to the dimensions of the orbital. f I. for a normal He atom with two electrons having quan- quantum number is related to the geometry or the shape of the orbital + tum numbers n = 1. corresponding to I values of 0. s c a n have only two values 4 and .3). On the other hand. 3 Polar coordinates r . Implication of spin quantum number is emphasized by the values from 1. and m which have integral values as required by + + l/s(s 1) h/2x..1.9. d.11. they are degenerate. These quantum numbers are: is assumed t o be an intrinsic property of the electron.g The wave function for a spinning electron is. 0.2. e .1. m . i.2 . Figure 2 . I= 0. . 4) = R ( r ) O (0) 0 ($1 angular mamentum ( L z ) in the direction of the field. . Another very fundamental concept which has to be introduced for systems with more than one electron is the spin quantum number s.. m due to the motion of the electron in its orbital. n call have metals. $)=R(r). This For example. H and b. for an electronicaliy principal quantum number n. then the two electrons must differ in their spin. f2. f. one electron shall be in s = 4 state and and is delloted by the symbols s. the concept of spin quantum number cannot be deduced from the Schrodinger n: the principal quantum number indicates the energy state of tho equation. since now the two electrons reside in two different energy states. n values differ the two electrons may have the kame spin values. This generates an angular momentum which is a vector quantity of magnitude The solutions of R (r) O (0) @ (4) equations introduce the three quantum numbers n. is a vector quantity whose value i$ given by 2 / 1 (1 + I ) h/2n. Angular momentum values are the same. Since it the quantum theory. R and + and factorization of total wavefunction. written as whenn=l. each orbital of given values of n and 1 is (21+ 1). .e 2 / r . I. p.e. (n . An orbital to explain the doublet structure in the emission spectra of alkali of number n will h a ~ ne nodes including one at icfinity. since in that case it m: the magnetic quantum number defines the orientation of the orbital can be resolved into three independent equations each containing only one in space and is effective in presence of an externally applied magnetic variable: field (Zeeman effect). If n. . The square of the angular 2 . It corresponds to the component of the Y (r. e. s: the spin quantum number arises due to spinning of an electron on V ( r . I . . 2.. I . Pauli exclusion principle which states : No two electrons can have the I: the azimuthal or orbital angular momentum quantum number arises same ralue for all the four quantum numbers (n. FUNDAMENTALS OF PHOTOCHEMISTRY NATURE OF LIGHT AND NATURE OF MATTER 19 18 same energy. . given by . 5 ELECTRONIC ENERGY STATES OF ATOMS momenta are eigenvalues of the angular momentum operator L2: The hydrogen atom has a single electron confined to the rlelghbourhood of the nucleus by a potential field V..4. i. The solution of the appropriate Schrbdinger equation becomes possible if the equation is expressed in polar coordinates r . co. 2.e. o (+ 4) is designated as a and o (. etc.(n-1) n=rl coordinates only. The possible values of 1 are governed by the the othsr in s= -+ state.e(O)cP ($1 an axis defined by an existing magnetic field.

with s. there are more than iE 2" one possibilities for such interactions. 312. !' L .12) .. With only one. D (L = 2). the possible interactions are: d .I L-SI (2. For each electron. with s. for an s electron the absolute value of j = 4. the possible values of L and S are: . and s. -VC lj 5 C) I " u rn I I P N . . to give j2. . d s ( s 1) h/2n.$o -- m 4d V) except for 1 = 0.11) (2. the vector addition is carried out one by one LID m 3 to get the total L. I).. 1- * c .. electron . ? .. (11 la . Therefore. d. and j. and I. The type (2) spin orbit interaction is known as the j-j coupling. - 0.3) similar to lower case symbols. These j values further . From the vector addition rule and the constraint that the . I S1 . 0 1 8 2 ." E 2 2" . For sodium atom with one electron in the outer shell. j can have values (I + s) >J > (1 . to give S. whcn 1 = 0 . f O O O for oue-e1e:tron atoms. there + can be only two values of j for any given 1 state: j = 1 4 or 1 --4.. .1 .-D LI u between L and S to give J.13) -c C) 0 -5 C c For N number of electrys. There will be 2 s 1 values of J when n_ -1 + L > S and 2L 1 values when L < S.e. Y 5 I 0 I -? C I C) I predicted by the vector addition rule and can have as many possibilities as C E E t E E the quantized orientations of the orbitals given by the values of m. s m o g o o s o d 0 X 0 0 0 0 D o d o should not be confused with the spin quantum number S for multielectrnn system and s for individual spin quantum number.-. In a completed shell or a subshell 2 2 the contribu'ions of individual electrons cancel each other and the total - . with I.I). and s. 512. + vectorially add to give the resultant as z/ j ( j 1) h/2q where j is the total angular momentum quantum number. (!+ turn. p. z e B values must differ by one in the unit of h/2x. FUNDAMENTALS OF PHOTOCHEMISTRY NATURE OF LIGHT AND NATURE OF MATTER 21 20 2.. followed by interaction between j. The symbol S when L = 0.in the unfilled energy shell.- L L1 2 The interactions of type (I) are known as L-S coupling or Russell-Saunders d coupling. s. For two electrons in an unfilled shell where L 2 the orbital angular momenta are denoted by I.12 I + + s = (s1 sz). the orbital angular momen- + + E 25 7D c a.-*3 1. . c4 n rr P (L . J = L + S . I P*. and spin angular 2 momenta by s. . to give L. i. to give J.s). The resultant angular momentum can be C. In the same way the total S is obtained.-2 -2 yl I? $ angular momentum is zero.. For the one-electroo system. to give j. followed by interaction (1) 4i . . - n v t N LO q N 7J For multielectron atoms the symbols for L values are: S ( L = 0). .- V) - -0 m (2) 1. o .11. The two are 0 e + finally coupled to get the total J.2 + + .1 Interaction of Spin and Orbital Angular Momenta The spin and orbital angular momenta of the electron are expected to interact with each other. . 41 ( I 1 ) h!2z and the spin angular momentum. possible j values are 112." = u 0 a = 4 S =k I bU s.5. T %j When the number of electrons is more than one. with s.8 2 I + (2. 1 1. etc. & d L = (11 1 2 ) . or s. and 1. F ( L -. L + S .

hence it is a triplet energy state and the spins of the two valence electrons must be parallel ( S = 1) and the particular value of J is 1 (J= 1). the energy state may be represented by J value alone as this is now a good quantum number.or 3 2P812 which are split due to spin-orbit coupling. for four-electron atoms singlet. ( I i si .. triplet and quintet states are generated and so on. 2.. for three-electron atoms. has a pair of electrons with opposed spin in the Sorbital.. singlet and triplet states arise. .n values that are obtained by vector addition of orbital and spin angular momenta are energetically different. 6aP. 5 ) .14) where li and st are one electron orbital and spin angular momentum numbers respectively for the ith electron and i can be 1. the most stable state is the one witb the largest L value.21. For one-electron atoms only doublet states are possible. for two-electron atoms. The complete description of the energy state of an atom is represented by the term symbol. the two closely spaced lines are observed in the emission spectrum. RULE2 : Among the levels having the same electron configuration and the same multiplicity. Since a normal mercury atom. These are the well known D lines of sodium (Figure 2 . Spin-orbit interactions muse splitting of the energy states into ( 2 s f 1) values. For example. 3. The various ter. etc. (six triplet Pone) state of mercury signifies that the total energy of the state corresponds to n = 6.I ) . where a 6s electron is promoted to a 6 P state. (lj si . the sodium atoms can be promoted to the doublet levels 3 2P. Odd number of electrons give rise to even multiplicity. These are known as the m14ltiplicityof a given energy state. this must be an excited energy state. doublets and quartets can occur. the orbital angular momen- tum is L = 1. those with the highest multiplicity will be the most stable. In the same way. In those cases where the j-j coupling is observed. A suitable guide for energy level scheme is provided by Hund's rules as follows: RULE1 : For terms resulting from equivalent electrons. When such atoms return to the ground state. 1 li . 4. . the multiplicity is three. . The j-j coupling is observed for heavier atoms ( Z > 30).22 FUNDAMENTALS OF PHOTOCHEMISTRY NATURE OF LIGHT AND NATURE OF MATTER couple to give total J.. whereas even number of electrons give rise to odd multiplicity.si 1 (2. + + + jj = (11 sj).

0 I (unpaired spin) (paired spin) I2s. the f electronic shell is being gradually built up. e.spa 8sl I1 L-2 L-1 L=O np S-0 S=O S=O No electron~c lnteract~on st s2 coupling '1 1 2 coupl~ng L -S coupl~ng Magnet~c f ~ e l dpresent J-2 J=l J=O (21 t 1 ) levels Energy state lpl lso Figure 2 . 0 values that can be assumed by the magnetic quantum number M ranging S= l . Wiley.t.1 ) . From Hund's rules. 3.3. I.6. then the state witb the largest value of J is the most stable. I L=(1+1). states since they are obtained for the combination 1. 6 Energy levels For the electron configuration (np)z. These are schematically shown in Figure 2. ( 1 + 1 . when L = 4 and S = 1 Similar splitting can occur in the presence of an electric field typically (iv) The ewrgy levels of rare earth ions LaS+. 8Poand 'So. The Pauli principle excludes all the three sD Eyring. The multiplets of the former are called normal multiplets and those of the latter as inverted multiplets.4 . The allowed states for C are ID.l J. Il = 1. 4. 2. For p electrons. . 3.= 1 and la=2 No. (ii) if the subshell is half or more than half filled. 2p2. 1.l 1/ tr~plet The possible J values are derived below: II level L=2 L=l L-0 '1 S-1 S-1 S= 1 II J = 3. carbon. In rare earths or lanthanide of strength > lo6 volts cm-I (Stark effect). = 1. SPe. = 1(L = 2) and 1946. 'PI. illustrating spin-orbit coupling and Hund's rules. 2s2. sDl spa9 8pl.1. f. I S=+t+t-1 and S = + f . The extent of splitting of ions.2. (Adapted from There are ten possibilities. I I Hence. The number o f f energy terms is proportional to the square of the electric field strength. sD2.2 . These correspond to the number of L = 4 .2. the ordering of these energy level willbe: SP(largest multiplicity) < lD (largest angular momentum) < 1s. O - from + J > M > J (Zeeman effect). 1. (iii) Interaction between two d electrons In the presence of magnetic field a further splitting into (2J+ I) I. I Only the two electrons in the p orbitals need be considered. l ) O I The last combination is - ll l2 or (1 .g.2. J = 5. z2 = 2 equispaced energy levels occurs.. The electronic configuration of carbon atom is: ls2. the state with the 'smallest value of J is the most stable. electrons for the first nine members of the series is given as: (ii) Interaction between p and d electron ce3+ p?+ Nd3+ pm8+ Sms+ Eu9+ cdS+ Tb8+ Dy3+ I. Walter and Kimball. off L ---. Is2 and 2s2 form the I completed subshell and hence do not contribute towards the total angular momentum.2 ) .1. 'T7: 1 singlet \ Examples 1 level '\ I \ ( i ) Interaction between two p electrons of C atom: I \ . = 2.1) = 0 I For spin vectors. ( 1 + 1 . electrons 1 2 3 4 5 6 7 R 9 .0 J= 1 II 11 Energy state 8Ds. $IATURB OF LIGHT AND NATURE OF M A m R 24 FUNDAMENTALS OF PHOTOCHEMISTRY RULE3: In the case of states with given L and S values two situations arise: (i) if the subshell contains less than half the number of electrons.) hence spins must differ to give singlet state. Quantum Chemistry. New York.

5. the lowest level being 7F6. For sodium atom. 2 s = $ = 3. &3. But since the subshell is more than half-filled. Such a diagram for Hg atom is given in Figure 2.8. The singlet and triplet manifolds are separated as they are forbidden by spin selection rules. These nuclei can vibrate with respect to each other and can also rotate around the molecular axes. Lz = 3.7 Energy levels of trivalent rare earth ions. But since the subshell z&. Sinha-"Fluore. CNR Rao and JR Ferraro. Eu3+ and Tb3+.P. Since vibrational and rotational energies are also quantized. Tb3+ with 8 electrons the ground The transition between the possible electronic energy states is governed state is again 7FJ.3. Gd3+ in which the subshells are just half-filled. therefore. -11. Quantum mechanical justification for this rule is given in the next chapter. This selection rule is known as Laporte's rule. The differences in quantized energy levels Figure 2. They are indicated by dashed lines in the diagram.4. 6 electrons occupy separate m states all with spins parallel: 2. for vibrational energy and those for rotational energy arc respectively scence and Laser Action in Rare Earth Chelates" in Spectroscopy smaller by nearly 10%and 10' times than those for the electronic energy in Inorganic Chemistry Ed. therefore. An = any value (ii) S can aombine with its own value. maximum multiplicity is (2 x 3 1) = 7.) .0 2. These ions are para- 0.7 gives the In an electronic transition : (i) there is no restriction on changes in n. i. the ground state of Eu3+is 7 F ~ . Figure 2. 3 + 3 . NATURE OF LIGHT AND NATURE OF MATTER 27 26 FUNDAMENTALS OF PHOTOCHEMISTRY An f shell (1 = 3) can accommodate 14 electrons. the ground state is an F-state.& 1 (iv) J can vary by 0 or f 1 except that J = 0 to J -0 transition is not allowed.5.1. 32P.3 =6. And J = 3 + 3 . 3 . as for example..1 . f2. 2. is more than half-filled for oxygen. AL = 0.The lowest level of the multiplet is 7F0 according to Hund's rule. The values of m are enwgy level schemes for SmJ+. the transitions between 6lS and 63P states of mercury. .. The wavelehgth associated with each transition is indicated in A units. The allowed transitions are between adjacent columns of energy states.3P0. For. inverted by certain selection rules initially derived empirically.e. 3 3. f 1 (except 0 -/+ 0) A basis for these empirical observations is provided by quantum mechanics according to which an odd term can combine with an even term and vice versa..12 level lies below 32P31. A J = 0. they give rise to discrete energy levels which can be calculated from the Schrijdinger equation.6 THE SELECTION RULE Hence.. For europium ion in the ground state.B.+ SP. (A. Let us take the cases of Eu3+ and Tb3+ on either side of magnetic.2 Inverted Multiplets Oxygen atom with p4 effective electron configuration has terms similar to those of carbon with p2 effective configuration. Under certain conditions they do occur with reduced efficiency. These are: multiplets are obtained. A S = 0 (iii) L can vary by 0 or f 1 unit. but for chlorine atom the order is reversed. the multiplet manifold is inverted 3P.. The case for TbJ+ is already mentioned above.. A convenient mode of representing these selection rules is the Grotian diagram for the energy states of an atom.2.7 DIATOMIC AND POLYATOMIC MOLECULES Molecules differ from atoms in having more than one nuclei.

it should be possible to obtain the electronic energy levels of the molecules as a solution of tht: Schrodinger equation. the hydrogen molecule ion. ~+=C.9. The molecular orbitals or MOs are obtained as algebraic summation or linear combination of atomic orbitals (LCAO) with suitable weighting factors (LCAO-MQ method) Y M O = C ~ ' $ I + C ~C343-k ~~+ (2. . is the coefficient of the vth atom whose atomic orbital is described by the function 4. The electronic transitions require energie5 in the visible and ultraviolet regions of the electromagnetic radiation and are accompanied by simultaneoils changes in the vibrational and rotational quantum numbers. that is. At the equilibrium distance re.= c34. Wavelengths are in A units. the exact solution has been possible for the simplest of molecules. This equilibrium distance is identified as the bond length of the molecule and the curve is known as the potential energy diagram. Hz+ only. then no bond formation is predicted and the potential energy curve shows no minimum. If no attractive interaction is possible. the splitting will be unequal. = C. the changes associated w ~ t hrotational transitions only are observed in the far infrared region ana those with vibration and in the near infrared. the corresponding energy levels will be equally above snd below the atomic energy level.~A+C~+B (in-phase) v.. Hz+. Therefore. 0 A and B : 0 Figure'12. A simplifying feature is that because of the much larger massof the nucleus the motion of the electrons can be treated as independent of tbat of the nucleus.16) = ZC"4" where C. molecule. = C. For heteropolar molecules. and with some approximations for the H. if inter- electronic and internuclear cross-coulombic terms are included in the potential energy for the Hamiltonian But the equation can be solved only if it can be broken up into equations which are functions of one variable at a time. = C.C44B (out-of-phase) For the homopolar diatomic case. the electrostatic attraction terms balance thz repulsion terms. For the simplest molecule. there are two possible I I modes of combinarion for the two Is orbitals of the two H atoms. C.8 Grotian. In principle. The variation of total energy of the system on approach of two atoms towards each other to form a diatomic molecule when plotted as a function of internuclear distance R is given in Figure 2. Even with this simplification.4 . NATURE OF LIGHT AND NATURE OF MATTER 29 FUNDAMENTALS OF PHOTOCHEMISTRY levels. This is known as the Born-Oppen- heitpier approxitnation. The wave functions for the molecular systems are described in terms of the atomic orbitals of the constituent atoms.diagram for Hg atom.

the wave function changes sign.10 illustrates the construction of MOs by bonding and antibonding combinations of s and p atomic orbitals. It can have values 0.x . (a) Attractive curve-bonding interaction.8 SPECTROSCOPIC TERMS FOR ELECTRONIC STATES a point x. 9 Potential energy curve for a diatomic molecule.. Figure 2. . FUNDAMENTALS OF PHOTOCHEMISTRY NATURE OF LIGHT AND NATURE OF MATTER Bond length Internuclear dlstarrce r In k Figure 2 . As in the case of atoms. . bonding and antibonding electrons : - with mass 2. etc. A o orbital is nonbonding bonding antibonding symmetric with respect to rejection on a plane passing through the mole. helium atom oxygen molecule with 16 electrons. and for a single electron. The component of the when the coordinates are . represented by a. etc. the ground state can be represented in terms of nonbonding inner electrons. x . For a g orbital. z on the left side of the inversion centre is transferred to the right side.y.~Z&' plane perpendicular to the bond axis. (b) re~ulsive curve-antibonding interaction. r---- r-- cular axis. of the higher AOs. For a 11 orbital. These subscripts are useful angular momentum in the direction of the bond is now more important for centrosymmetric systems only such as homonuclear diatomic molecules. The resultant MOs are identified by their symmetry properties with respect to their symmetry elements. 6. Y(X)= -v(-X) The spectroscopic term symbols for the molecular case can be obtained.10 Formation of molecular orbitals (MOs) from atomic orbitals The higher MOs are formed by in-phase and out-of-phase combination (AOS).z. The letters g and u stand for Mulliken gerade or symmetric and ungerade or antisymmetric function respectively notation: K K zo: yo: xa: wxt vxi under the operation of inversion at the point of symmetry located at the bond axis. . f1. Figure 2. y. r--A-.yxu)' (~P. the wave function does not change sign if 2. is designated by A. A has the same meaning as the quantum gradually fed into these energy levels obeying Pauli's principle and Hund's number m in the atomic case as can he shown by compressing the two rule to obtain the complete electronic configuration of the molecule. A x orbital is antisymmetric to this operation and has anodal ( (1 ~su)' ( 2 ~ ~ g ) ' ( 2 s a ~ (2pag)' )~ (2px. the available electrons for the molecules are f2. For hydrogen nuclei to the extent that they coalesce to give aHe.

11. Il. If one electron is excited from 2pxu to a partially filled From Hund's rule the ground state of 0. 3C. The strong ultraviolet absorption of oxygen. Jinding the electron.. the slates respectively. An electronic orbital is defined as that 17olu~eelemevt . and lC-/ states exist.. and the higher excited states are alA. Hund's rule permits both the singlet and triplet According to convention. symmetries xu x x. The two quantities combine shell will always have 2 symmetry. The unpaired electrons in the ground state account for the paramagnetic property of the oxygen molecule.32 FUSDAMEN'I ALS OF PHOTOCHEMISTRY NATURE OF LIGHT AND NATURE OF MATTER 33 as in the case of atoms. can be 0 or 1 giving the spectro. A = 1 . = XU+. the total spin value can only be 0 from Pauli's principle and a doubly degenerate At this point it is important t o distinguish between the terms electronic state and electronic orbitals. orbital.molecule in our environmental photo- of excited singlet oxygen 'A. Therefore. TABLE 2. B.1 1 (t+).1 k2. A = CAI = 0. and b1C.9 %) of ]A. The other two 2px.- when the molecule is centrosymmetric. 96 kJ (22. and the spectroscopic terms are Direct product rule for assigning molecular symmetry from orbital symmetry represented as Orbital symmetry h. For example.. by the summation of all A's to give the total Jn general. For the 0. etc. C . The Table 2.. A. onset of 'vacuum ultraviolet region' of the spectrum.+h==A Molecular symmetry For example. C. and 3C.. the electronic state of a molecule can be obtained from the . The term symbols for A = 0. and ]C. the nonbonding inner shell electrons and the set of bonding electrons do not contribute towards the resultant angular momentum because they form the completed subshell..of space in which there is a high probability (99. 2px. Thus. c. consider the 0. h = + 1 and A = CAI = 0. f1.will be 3Z. The possible states lA.. It is calculated from the one-electron wave function scopic terms 'C. b. S = Cs. molecule again. the principal quantum number n has no meaning. the ground state is denoted by the symbol y. Schumann-Runge continuum is associated with the electronic transition etc.l+ in thermal and photochemical chemistry. various energy states and the corresponding potential functions oxidation by molec~~lar oxygen is being gradually realized. Since the interaction between electrons is quite significant.7 kcal mol-l) above it. and those of different multiplicity by small letters a. When a C state is obtained from combination and is assumed to be independent of all other electrons in the molecule. When A 2. and S = Cs. A = CAi and the direct product of the symmetry of the occupied orbitals. the g or u character of the product - vectors are in opposite or in the same direction. with the electronic configuration as given above. From the consider the states of the molecule involved in such electron promotion. each orbital will possess an odd electron. etc.. etc. molecule. xu orbital. + of h > 0. = is a. requirement that the total wavefunction including spin should be anti. 3AUa11 are higher excited states of the same multiplicity as the ground state by Possible. which marks the A . the ground state of oxygen in T3C.5 kcal mol-l) and 163 kJ electronic state associated with this configuration will now have the (37. Only the contribution of the two p electrons in the half-filled antibonding MO is important.angular momentum number in the direction of the bond axis. 321f. are.Z'.. . for example. For the p electron. the term symbol for 1s electron in H$ with A = 0. are given in Figure 2. orbitals. Because of the degeneracy of this orbital more than one combinations of angular momentum vectors are possible. it is important t o axis whereas the (-) sign indicates that it is antisymmetric. l a u . state exists. Since the two odd electrons now For MOs.1. The role Because of the importance of 0. When A = 0. A doubly filled total spin angular momentum number S = Csl. respectively are C. and IC. Other combinations are given in + vectorially to give resultant angular momentum number Q = ( A S / . . the+ Electronic states signify the properties of all the electrons in all of the degeneracy of the state is destroyed by interaction to give C+ and C. A (+) sign indicates that the MO is symmetric with transition of an electron from one orbital to another will result in a change respect to the operation of rejection from a plane containing the molecular in the electronic state of the molecule.. + total multiplicity is again given by ( 2 s 1).1 (-+ t)or A = . A. It has 4 electrons in the symmetric (antisymmetrization principle). Occupy separate orbitals. f 2 according as the momentum is given by : (i) g x g = u x u = g and (ii) g x zt = tr x g u. respectively. states of the above symmetries and 'XU+. only 3C.

group C. any physically observable property of are five kinds of symmetry operations which are necessary for classifying the molecule must remain unchanged by the symmetry operation. which does not change during these operations.- -0 Figure 2.12 Elements of symmetry for HaO molecule.. changed by any symmetry operation of the point group. Let us take the simple molecule. of the molecule is one such property and the Hamiltonian must be un- (i) Rotations about an axis of symmetry: C. in contrast to translational symmetry observed in crystals. NATURE OF LIGHT AND NATURE OF MATTER 35 FUNDAMENTALS OF PHOTOCHEMISTRY (v) Identity operation or leaving the molecule unchanged: I.. planes and centre of symmetry are known as the elements of symmetry. physical behaviour in general. a branch of mathematics. . molecule has indistinguishable geometry at two positions. Since each of sources). It has two planes of mirror symmetry. possible if the symmetry operator has values f 1.11 Potential energy diagrams for molecular oxygen electronic energy states and the absorption spectrum of oxygen molecule.9 ORBITAL SYMMETRY AND MOLECULAR SYMMETRY As already evident from the previous section. the only (iii) Inversion through a centre of symmetry: i. the centre of gravity of the molecule. On complete rotation of the molecule through 360". This is cnly (ii) Reflection in a plane of symmetry: a. water to understand some of these terminologies (Figure 2. therefore. 360°/2 and 360". bisecting the HOH bond angle. ap passing through the plane of they can be treated by group theory. possible wave functions of the molecules are those which are either Rotation about an axis followed by reflection in a plane perpendi. the of the behaviour of atoms or moleculesunder certain symmetry operations. Energy a point group. symmetry properties of a molecule are of utmost importance in understanding its chemical and Figure 2. The selection rules which govern the transition between the The water molecule has a two-fold ( p = 2 ) rotation axis along the energy states of atoms and molecules can beestablishedfrom considerations zdirection. such that an observer who has not watched the operation can. These A symmetry operation is one which leaves the framework of a molecule three operations together with the identity operation I form the point unchanged. H c r z b e r ~bands il -O P n. symmetric or antisymmetric towards the symmetry operations of the (iv) cular to it ( a 1 ~ 0called improper rotation): S . there is a group of operations and. Hence the designation point symmetry. to which the water molecule belongs. There physically equivalent configuration. The geometry of the molecule is governed by the geometry of the symmetry operations of the point group carries the molecule into a the orbitals used by the constituent atoms to form the molecule.12).. the molecule and the other ax. All these elements intersect at one point. say. The axes. and spectroscopy and photochemistry in particular. For'each type of symmetry.sphcrjc O 2 bands 1 \s - fnlrared atrnospher!~bands 3. not tell that an operation has been carried out on the molecule (of course In the molecular orbital theory and electronic spectroscopy we are . 2...lie presupposes the structure of the molecule from other experimental interested in the electronic wave functions of the molecules. Hence.

Similarly. . 1. Species A is symmetric with respect to rotation about the z-axis and species B anti- symmetric. p.1.36 FUNDAMENTALS OP PHOTOCHEMISTRY NATURE OF LIGHT AND NATURE OF MATTER 37 group.13b the molecular plane is the plane of the T-=translational transformation.+ 1. this point group the symmetry operations are I.. orbital on oxygen atom in HaO: symmetry behaviour with respect to the operation of inversion. 1. p. Other possible combinations are 1.1 as for px orbital and cu I CzZ an i + - 1. + 1 for the operations I. The identity operation also leaves TABLE 2 . taking into consideration the symmetry of the molecule and the atomic orbitals used for their formation. If there are more than one A and B species they are further given numerical subscripts.2 +1 +1 -1 -1 Rs The x-orbital system of butadiene has a node in the plane of the molecule bl* Bl +1 -1 +1 -1 Ts R" in the bonding combination and also contains oh plane ((I. symmetries of oxygen atomic orbitals are Let us examine the behaviour of p. In Figure 2. A1 +1 +1 +1 +1 Ts ~ 2A . orbital In water under thesymmetry operation of the point group C.2 The character table for the point group C. by convention small letters are representations for electron and antisymmetric behaviours are usually denoted by + 1 and . I ci a:' o r T R - a. 1 3 (a) symmetry ofp. called the character table. (b' Symmetry of 2pn bonding MO of *trans- . The symmetric In column I. .". TABLE 2. provided the wave functions are nondegenerate. + I. reflection on otX following symmetry species can be generated: changes the sign and hence is . for the point group Cp. The net symmetry is obtained by the direct product of the symmetry species of the occupied orbitals. Thus symmetry operation. For centrosymmetric systems wlth a centre of inversion i. R-rotational transformation. If we consider the two px-lobes above and below the paper and . Rotation around the z-axis changes sign of the wave function. symmetry and if all the orbitals have paired electrons for any given molecular configuration. Ci. (Figure 2. and are called the character of the motion with respect to the four distinct behaviour patterns are called symmetry species.13a). and the antisymmetric and has the character - 1. orbital The character table for the point group Cu transforms as + + 1. orbital is The set of MOs are generated. + 1. oh and i. Under butadiene: symmetry C2b.. On the other hand. CZ. C. All this information can be put down in a tabular form. the state is totally symmetric and belongs to the species A. Thus All doubly occupied orbitals have a. 3 + the orbital unchanged and hence is 1. - +I -- -1 -I +1 Tv Rz the z-axis. paper. The molecule group C 2 . hence under Cz.1.. + . These pectively. subscripts g (symmetric) and u (antisymmetric) are also used to designate the Figws 2 . 07 and 0:'.13b). 1.) horizontal to bssB2 .. whereas a': transforms the orbital into itself and hence has the character + 1.. trans-butadiene belongs to the point group C 2 h (Figure 2.1 res- orbital symmetries and capital letters for molecular symmetries.

. Some of these MOs are the most common method is to denote them by their multiplicities.g. unusual properties of water and is responsible for the native structure of biomolecules such as deoxyribonucleic acid (DNA). (b) n-orbital (nonbonding). and triplets TI. pure atomic orbitals and do not take part in construction of MO. The pair of electrons occupying these orbitals is called lone pair electrons or nonbonding electrons. e.H. (Figure . e. strong than a-bonds but give rigidity to the molecule. II.N. e. When They participate in double (as in ethylene) or triple (as in acetylene) bonds details of the electronic structure of states are unknown or not necessary.g. orbitals or hybrid orbitals like sp. in general. specially for designating energy kvels of polyatomic organic compounds. This form of description is less precise than the symmetry notation but is very convenient for photochemical purposes. C ' z ~ . They are also involved in the formation of coordinate dative bonds. e.g. N n2P. (ii) Saturated molecules with q and nonbonding n-MOs..15. (a) I-orbital (lone pair). respectively.TI. (iii) Unsaturated molecules with a and x-MOs. using a pair of electrons with antiparallel spins. Other important ketones. Z. The x-bonds are less excited states as S. Tz. The ground state is denoted as So and higher system of double bonds. The doubly degenerate single electron MOs are designated by the aromatic hydrocarbons. hence described as n or nonbonding. the line of centres. Types of "lone pair" electrons in heteroatonlic molecules described by Kasha are given in Figure 2. They are tion by the quantized component of the orbital angular momentum along formed by the overlap of p. Figure 2. etc.. The n-MOs are. Figure 2.. S. The lone pair electrons have far-reaching importance in H-bond formation which determines. a* and x*-MOs are antibonding equivalents or a and x-MOs..2. CH. M. pyridine. or hybridized orbitals of similar symmetry. In general.Sz. CO. symbol e and the triply degenerate by t. A clear picture of all these different types of M o o can be obtained . The x-MOs have a nodal plane in the plane of the molecule. butadiene and benzene.. The a-MOs are bonding type with axial symmetry.14). p. amines and other heterocyclic compounds symmetry groups are T d and Dsh. &localized over a number of atoms as in molecules containing conjugated S (singlet) or T (triplet). H. A is possible for linear molecules only.. '2p. They form strong single bonds with two spin Representation by overall symmetry of the molecule is the most useful paired electrons localized between the combining atoms. 0 carbons. in such cases they are designated as I-orbitals. sp3. etc.Ss. B2H.I. spa. four types of molecules can be identified. way of designating the energy states of a polyatomic molecule. the paraffin hydro. The characteristics of the lone pair electrons can vary if their nodal plane has a suitable geometry to conjugate with the x orbitals of the rest of the conjugated molecule. e. etc. S1. symmetry species are termed E and T.38 FUNDAMENTALS OF PHOTOCMTRY NAfUkE OF LIGHT AND NATURE OF MATTER 39 the z-axis perpendicular to the plane of paper. "rpZ N (i) Saturated molecules with o-MOs only..Tg state of a typical organic molecule. Kasha has evolved still another system ofnotation in which electronic states are expressed in terms of the initial and final orbitals involved in a transition. Classifica. Since now lone pair orbitals are no longer nonbonding. x and n-MOs.10 NOTATION FOR EXCITED STATES OF ORGANIC by overlap of s or p.. respectively. aldehydes.. along MOLECULES the direction of the bond.g. They are formed 2. the px-orbital of butadiene is found to belong to the symmetry species A.g.. NH. for example.O. C.14 Relative energies of singlets So. containing 0. Corresponding molecular (iv) Unsaturated molecules with u.15 Types of lone pair electrons.

etc. E. dmmediately. x * ) . The possible combinations are given in character. o*). Figure 2. a-skeleton of the hydrocarbon is perpendicular to the wave functions ofn-MO. The energy increases with the number of nodes so that occupied. AOs need be considered for the formation of x-MOs of interest energy state of the molecule changes.16). various photophysical processes that may occur after the initial act of absorption of radiation. Once the electrons are orbitally decoupled on excitation. x*). x * ) state plays a very important role in the photochemistry of transitions in formaldehyde molecule. one can observe the similarity of the wave functions thus Both S singlet (spin paired) and T triplet (spin parallel) states are possible. their approximate energy levels and types of The (n. etc. carbon utilizes sp2 hybrid orbitals also possible but require much higher energy and may appear in the far to form a-bonds and the pure p. x known as Jablonski diagram (Figure 2.1 Unsaturated Molecules with ~onj&ated System of Double Bond transition depending on the final energy level. obtained with that for a free particle-in-a-box. C uses sp2 whose energles are dictated by the nature of the molecule. The character. (a -t o*) transitions are In simple conjugated hydrocarbons.18. < E. the possible energy states are '(n.. When excited to x*-MO. the triplet state is the lowest energy excited state. orbital of oxygen (2s A 0 is supposed to be localized on oxygen). carbonyl compounds and many heterocyclic systems. x*). 2p. it may be a ( x + x*) or (x -t o*) 2. spin restrictions are lifted. x * ) . These states are designated as for photochemists. The energy values can be Thus. Such a diagram is also two by carbon are accommodated in the three lower energy levels of a. (n.C=O. (x. The six electrons. and may have singlet or triplet contributed by 4 carbon atoms. In the ground state when all the bonding MOs are doubly Figure 2. of 0 is nonbonding. According h brid orbitals to form olbonds with Is orbital of 2 hydrogen atoms and ?p. Let us consider the case of butadiene with px A 0 (n. n*). Figure 2 . x*).40 FUNDAMENTALS OF PHOTOCHEMISTRY NATURP OF LIGHT AND NATURI? OF MATIER 41 from the discussion of the formaldehyde molecule: H. the (n -+ x*) transitions have low probability and hence weak n electrons are most easily excitable and give rise to the longest wave absotption bands. '(x. absorption band. maintaining the order of energy values. the only p. The ground state is diagram (Figure 2. Since the UV region. In conjugated hydro- carbons ( X -+ x*) transitions are most important and give intense An electron from any of the occupied orbital can be promoted to characteristic absorption bands. 1 6 Molecular orbitals.).17 Jablonski diagram lor (rc. State diagrams are represented with all the singlet levels expressed as horizontal lines one above the other and the triplet levels are drawn slightly shifted formation of > C = 0 bond can be represented by the energy level in space. < E. Because of some overlap forbidden higher unoccupied level on absorption of appropriate radiation. < E. ( 0 .(a. When an electron from x-orbital is promoted. it is designated as (n-+x*) transition. On promotion of an electron from any of the occupied orbitals.17) and is useful in representing and n character. x*). o*). x*) and (n. approximately calculated from the expression . ' ( x . singlet and triplet states.10. Pure px AOs of C" and 0 form x-bonds. The to Hund's rule. x*). the Pauli principle predicts only the singlet state. four contributed by oxygen and arbitrarily assigned a zero value for the energy. orbital to give the n-MOs. Such transitions in aniline are represented as (I-+ a.

and 6.C = C . and ez. the free electron perimeter model has been found to be use- ful.20 Nodal properties of pyridine. type orbitals. The two electrons which formed the o-bonds in .(e2." lower two orbitals. The energy requirement for the lowest energy transi- tion is given by: Figure 2. The substitution of N lowers the overall symmetry of the molecule from D.19 Nodal properties and energy levels of benzene. The energy levels and nodal properties of benzene molecule are given in Figure 2.H is replaced by N. Both singlet and triplet states are generated by the orbital promotion of an electron. The MOs for inorganic complexes are obtained by combining AOs for . The MOs of pyridine are given in Figure 2.h to C2.18 Nodal properties and energy levels of butadiene. Pyridine is isoelectronic with benzene in which C .[ e2 "' "$ih2.7.-. if 1 the length of the molecule can be estimatedfrom the . 2.19. l Figure 2. In the ground state of butadiene.CH are now localized in a nonbondiog hybrid orbital centred on the nitrogen atom.and the degenerate el.. 1 . the 4 electrons will occupy the 'a.20. orbitals are split into a.bond lengths.11 ENERGY LEVELS FOR INORGANIC COMPLEXES . For benzene. A -t X* transitions are totally allowed These energy values can also be calculated from Hiickel molecular orbital (HMO) method.42 FUNDAMENTALS OF PHOTOCHEMISTRY \ \NATURE OF LIGHT A N D NATURE OF M A n E R Figure 2.

and the triply degenerate as t. The oscillations of the two fields are given by E. TABLE 2. the matching of metal orbitals andthe six ligand orbitals denoted by $. 2 . I.) of a transition metal. being antisymmetric to the operation of inversion are denoted tlu. the magnetic quantum number and m.k x ) .k x ) Hz = Ho Sin 27r ( v t . For an octahedral complex. complex of octahedral symmetry is given in the Figure 2. E LIGHT A N D NATURE OF MATTER ~ ~ A T U ROF 44 FUNDAMENTALSb~ PHOTOCHEMIST~Y the valence electrons of the metal ion with the AOs or MOs of the ligands. The energy level diagram for ML. The energy states of atoms are expressed in terms of four quantum numbers :n. The idea of field is wholly derived from its . The associated magnetic field vector H. the principal quantum number. Electromagnetic radiation consists of a n electric vector E directed along the displacement direction of the wave. AOs of the metal Ligand combinations Symmetry (L) specles (M) 4s (116)(+I + +2++a++(++5++6) atg 4 ~ s (112)(+1-+2) 4 ~ 9 (112)(+3-+4) flu ~ P Z (112) (96 . . the spin quantum number..$. symmetry. keeping the overlap and energy criteria i n mind. lies perpendicular to the electric vector and perpendicular to the direction of propa- gation. Electromagnetic radiation is a n oscillating electric field E in space ahich is propagated with the velocity of light. the additional concept of 'aethcr' is valueless and unnecessary.$6) 3dzs (1112) (-+I -+a -08 -94 -05 -+. The s-orbital has al. no two electrons can have the same values for all the four quantum numbers.21. .4 Suitable combination of metal (M) and ligand ( L ) MOs for a-bondi~lg in an octahedral complex (ML. According to Pauli's exclusion principle.) 3dXs.yr + (114) (91 +*-#a+ 4") go Summary 1. m. the azimuthal quantum number.4. . or s. = Eo Sin 271 ( v t . is illustrated in Table 2. The doubly degenerate set is designated as e. 3...measurable physical effects. for o-bouding. The triply degenerate p-orbitals. . The d-orbitals are symmetric to inversion and are hence of g symmetry.

Electromagnetic waves behave like particles in photoelectric effect. (iii) If the species is symmetric with respect t~ a Csoperation perpendicular to .T8.Ts. l ( n . 4. . n*). arc conveniently designated as 1 ( ~n*).magnetic permeability = dielectric constant the principal axis then subscript 1 (symmetric) or subscript 2 (antisymmetric) is added t o A and B (operation c:.\/& p E . and operation of inversion through this centre (operation i). obtained by L S or Russell Saunder's coupling scheme. (iv) Single primes and double primes are added to A and B when the species is symmetric or antisy mmetric respectively to reflection in a plane perpendi- k = l/A cular to the principal axis of symmetry (operation oh).. 7. 9. For multielectron atoms. common terminology. n*). singlet and triplet energy states 5 . L is the total orbital angular momentum - component obtained by the vector addition rules. So. The molecular orbitals (MOs) are formed by the linear combination of atomic orbitals (LCAO-MO method). is called a photon. doubly degenerate species as E and triply degenerate as T.). Electronic states of an atom or a molecule are obtained by considering the properties of all the electrons in all the orbitals. 1) to this operation are designated as B (operation C i ). It is useful to classify electronic states in terms of their symmetry properties as defined by the group operations pertinent to that particular molecular species. Matter is classically particulate in nature. 11. the term symbol for an energy state is represented as where S is the total spin angular momentum component obtained by the vector addition of the spins of all the valence shell electrons and (2s + 1) is the total multiplicity of the given energy state. 8. . The properties of the electrons in the unfilled shells are the main contributors. NATURE OF LIGHT AND NATURE OF M A l T E R and &/H.. and TI. according The wave property of matter is related to its particle nature by de Broglie's as they are generated by (n + n * ) transition or (n + n*) transition. The quantum of energy. limited by the Heisenberg uncertainty principle which may be stated as 12. the wave character of particle motion and quantization of energy become important when the masses of the particles become comparable to Planck's constant h. Sl. and Q is obtained by vectorial addition of A and S.etc. + 1) with respect to rotation about the principal axis C.S. Compton (v) For centrosymmetric molecults with a centre of inversion i. Photons travel with the speed of light c. possess a momentum hvlc. For most relation A = h/p. In saturated and unsaturated organic molecules. but it also manifests wave character. The energy states are expressed by the symbol 2s+1 where A = xA1 A. For diatomic molecules. 10. u are added if the species is symmetric or antisymmetric respectively to the E = hv. group theoretical nomenclatures are used. s(n. those which - are antisymmetric (character. Mulliken's terminology is based on the following rules (small letters are used for one electron orbitals and capital letters for molecular states) : (i) All nondegenerate species are designated as A or B. n*) etc. = . . We cannot extrapolate our knowledge of everyday macroscopic world to the world of subatomic dimensions. The Heisenberg uncertainty principle. subscripts g and effect and phenomena of absorption and emission. Our understanding of the interaction between light and matter is governed and triplet states. a(%. where A is known as the de Broglie wave length. the component of the angular momentum (1) in the direction of the bond axis is now important. (ii) Nondegenerate species which are symmetric (character. For imwJanic complex compounds. . are designated as A . are used for singlet and 6. and J is the total angular momentum quantum number.

radiation waves are cancelled out by destructive interference in all directions except that of rejection or refraction. But when vr z v. it becomes a source of electro- magnetic radiation. (b) elcctro- magnetic radiation wave. Under this condition a quantum of rsdiation or a photon is absorbed by the atom or the molecule. An oscillating dipole moment p (defined by 3 . (a) an oscillating electric field. field. we know that when a positive and a negative ~ W g oscillate e with respect to each other. is not close to that of the natural frequency v. THREE From electrodynamics. The dipole is generated in the direction of the electric vector of the incident radiation. The electric vector of the plane polarized incident radiation distorts the normal hydrogen atom in particle composed of positive and negative charges is b r ~ u g h tnear an electric. If now the . the 8stillations classically become 'free'. The secondary radiation thus scattered Rqiformly in all directions interferes with the primary incident radiation. MECHANISM OF ABSORPTION OF RADlATrON 49 jfthe field oscillates between the upper and the lower positions. When the field is applied from the upper side (Figure 3 . I). its spherically symmetric s state to a state which creates a dipole in the d i m i o n of the vector field.2 Mechanism of absorption of radiation by H atom. As long as the frequency of incident radiation v. The radiation emanating from the source is propagated 6 all directions like a sound wave from a ringing bell. and a resonance condition is established h e e n the two interacting partners (the photon and the molecule). the positive charge density is attracted towards it and the negative charge H('s) . the induced dipole will also oscillate with the frequency of oscillation of the field. the (laucillations are due to forced distortion of the molecule by the electro- hgnetic wave. The situation is analogous to the case when a for the case of a hydrogen atom (Figure 3. generating a dipole moment in the particle. of the molecule as given by its energy states.2). The oscillating electric field of the electromagnetic radiation ects in a similar fashion to create an oscillating dipole in the atom or the molecule with it is interacting. As a result. This is the mechanism of scattering of radiation by a Photochemical Interest @cle of molecular dimensions. The disturbed molecule becomes a source of flectromagnetic radiation of the same frequency as the frequellcy of the Emission of Radiation of incident radiation. The mechanism can be illustrated as follows atom or the molecule. density repelled. the electric field of the radiation tends to disturb the charge cloud around thc as tbe transition moment. H(2p) Figure 3. promoting it to a higher energy state.. Obviously it is a p state with a nodal plane nnn Electric vector Figure 3. 1 ELECTRIC DIPOLE TRANSITIONS the product of charge e times the distance of separation r between the centres of gravity of positive and negative charges) iscreated and designated When electromagnetic radiation falls on an atom or a molecule.1 Creation of an oscillating dipole by interaction between the charge cloud of an atom. A similar situation Mechanism of Absorption and bpplies to the present case.

1 is negligible in comparison to @Ik=. 1. can also be obtained from the Boltzmann distribution promotion to the upper state occurs with absorption of appropriate . The rates of On the other hand.50 FUNDAMENTALS OF PHOTOCHEM~STRY MECHANISM OF ABSORPTION OF RADIATION 51 perpendicular to the electric vector. at high frquency regions such as visible and near ultraviolet. rates will be-equal and we have Bnm Nn P (vmn) = A m n N m + B m n N m p (vmn) ( 3 4) On rearranging.@lkT The probability of return from m to n consists of two parts.5) < a d A. .2. Hence Rate of absorption = BnmNn p (vnm) (3.2) where Bnmis the proportionality constant and is known as Einstein's - Bmn A. Einstein in 1 9 1 6 treated the corresponding problem for quantized systems such as atoms and molecules in the following way. > Therefore.1 is spontaneous and hence independent of radiation density and the other proportional to it. When exposed to thermal radiation at temperature T. is proportional to the number of particles Nnin the state n and the density of radiation of frequency vmn. The ratio of the number of particles in the states n and m with energy En . From the condition of equilibrium between the rates of absorption and it will absorb the radiation and will thereby be raised to the upper state pmissioa. 5 ) and ( 3 . 3.. The probability per unit time that . Under the resonance condition. from ( 3 . the ratio of the two transition probabilities is small --. a system of accele- rated charged particles emits radiant energy. p ( ~ m n ) . then > whcn hv kT. According to Bohr's B w = Bm* theory. 7 ) and ( 3 . whcn hv kT. On the other hand.. 5 ) and ( 3 .. 6 1 .3) spontaneous emission has a large probability but that of induced emission where A. p (v). . This is known as an electric dipole transition..2 EINSTEIN'S TREATMENT OF ABSORPTION AND EMISSION ~olvipgfor p (v. + Rate of emission = Aan Nm B m n Nnt P (vmn) (3. B. P (vmn) +1 (assurmng Bmn= B.) and substituting for NnlNm. These opposing body radiation at temperature T (Sec. Considering only the first two terms. This condition i s obtained in the microwave region Nm Bnm P (vnm) md is utilized in the construction of masers (microwave amplihation by *mulatad emission of radiation). the two to a series expansion. it also absorbs radiant energy. the frequency of the absorbed radiation is given by Let us assume that the system is in the lower state n and exposed to a . one which Hence.. If IVm be the number of particles in the upper state rn Bmm P (k) - at any time t.A m n N n + Bmn P (vmn) (3.. law: radiation.@lkT . and A. we PHENOMENA have According to the classical electromagnetic theory. we have from equations ( 3 .respectively. we get Since hvlkT is small. and Em. is known as Einstein's coefficient of spontaneous emission and < h very small. At equilibrium. B.. 6 ) m. we know that processes are expected to lead to a state of equilibriu~li. Comparing ( 3 .) coefficient of absorption.1 Probability of Induced Emission a d Its Application to Lasers radiation of density p ( v ) defined as the energy of radiation per unit volume + between the frequencies v and v d v . we find Let us consider two nondegenerate stationary states m and n of a system. from Planck's derivation of energy density for a black absorption and emission are given by the classical laws. 8 ) . 3. with energy values E m and En where E m > En. &IkT can be subjected Bmnas Einstein's coeficient of induced emission.4).

But if a beam of radiation is generated system is the inherent possibility of bringing about population inversion. the impinging photon i s more likely to encounter a n excited particle than an unexcited one. If we denote 4J (x) as a function of x only and probability Bmnis low. the probability of induced emission in the visible region must or. of stimulated emission has found immense use in maser and laser The photon thus induced to be emitted has the same phase relation- technology. the numbers are governed by the Boltzmann distribution law. In the absence of a radiation field. an extra photon is added to the beam. practie~lly only the On separation of variables.3b). where Nn and Nm are the populations of the energy states n and m. To obtain the laser action or light amplification by stimulated emission of radiation. either through a pin-hole or by a little transmission (Section 10.52 FUNDAMENTALS OF PHOTOCHBMISTRY yi W&CHANISM OF ABSORPTION OF. absorption is preferred because Nn is large. respectively. The probability of induced emission is given as BmnNm p (vmn).15) The population of state m starts building up and after a time. This property known as pump radiation and the radiation which stimulates emission is known as laser radiation (Figure 3. Further amplification of this coherent emission is brought about in a resonant optical cavity containing two highly reflecting mirrors. one of which allows the amplified beam to come out. It is represented in one dimension as Figure 3. When Bmnis small. To each photon impinging on the it has phase coherence.3 (a) Radiation from a normal source-inwhdrent beam. then in the higher energy state. and (-h/2-i) the population Nm of the upper state m is in general small. The phenomena of absorption and emission can be handled mathe- matically by the time-dependent Schrodinger equation only. Under the circumstances obeying the unimolecular rate law and the emitted radiation is incoherent the emitted intensity will be larger than the incident intensity.Nm). which is equal to Y(x. depends Substituting on the difference (Mn . ship as the inducing photon. (b) Radiation from a laser source-coherent beam. be increased. This is (Figure 3.3a). The spontaneous emission is a random process system. On the other hand. When a stream of photons is allowed to impinge on such a system. the rate of such emission is expected to be small since where Y is a function of position coordinate x. the The radiation which promotes the molecules to upper energy state is energy of radiation is localized in a small angle of divergence and the intensity is preserved even on propagation tolongdistsnces. the populations of the two energy levels remain constant. RADIATION 53 The importance of induced or stimulated emission lies in tht fact that photon rather than its absorption. ----1 ha aZ+(x) --h 1 4J (x) 8xam 8. we have ground state is populated. The divergence of radiation in all directions causes loss of known as the laser action. thereby stimulating emission of a . is to somehow increase the number of particles Nm 40) as a function o f t only. and we have. For electronic energy states at ordinary temp-ratures. Therefore. even when the emission nonconservative system. with all the photon waves vibrating in the same phase (Figure 3. A photostationary Each side must be equal to a constant which is identified with energy equilibrium is established.4). One way to ' (slat) is the quantum mechanical operator for the total energy E in a increase the rate of phase-coherent emission. As long as the irradiation source is maintained E. and time t. For any given value of B. the rate of absorption becomes equal to the rate of emission. t ) = 4J ( 4 +(t) Brim.. whether absorption will teke place or emission stimulated.P +V(x)=---2xi + (t) at (3. the important aspect of laser light intensity on propagation.4). if by some means the population of the excited state is increased.

The description of the unperturbed system is given by the wave equa- tion including time where 4C0 is the Ha. The normalized general solution of this equation is 'Y = Z an Yn (3. Y n (x. of a definite field strength E. 3. t ) = (x) e-271Enrlh dnd the probability distribution function is given by. . These are the allowed states that are obtained as solutions of the time-independent Schrodinger equation.19) The time-dcpendent part disappears if wc consider the probability distribution in the same energy state.miltonian for the unperturbed system. Furthermore. the system comes under the perturbing influence of the radiation of a range of frequen- cies in the neighbourhood of v.4 TIME-DEPENDENT PERTURBATION THEORY On absorption or emission of radiation.(x) ez*lEnte e-2*IEnrlh d~ (3.22) n In this expression a. Let us consider two stationary states n and m of an unperturbed system represented by the wave function Y>nd Y i such that Em > En. Let us assume that at t = 0. t ) Y n(x.. It is therefore. a system goes from one station- sry state to another under the influence of incident electromagnetic radiation. Pa: an= 1. At this time. Y: (x.ygCHANISM OF ABSORPTION OF RADIATION The time-dependent part can be easily solved The total wave function for one dimensional Schrtidinger equation for the nth energy state is written as. are constants or weighting coeffcients which are not functions of x but may be functions of time r . the system is in the state n.. 1 ) dr = I +: (x) +. necessary to investigate how a system is disturbed or perturbed 50 that a transition is induced. This defines the concept of station- @y states.

. the perturbation theil being effective only during this period.-h 21ri a . < t c~ tz.' Yi d~ . For a given value of t. = 1 and am = 0. but a. equation (3.31). . we have at t = 0. n To evaluate the equation. t) (3.1). The The coefficientsan are constant for time t' alone...24j 8 p molecule and causes it to escape from its initial stationary state n.*'1 ~ c H A N I S M OF ABSORPTION OF RAD~ATION 57 as required for normalized systems. (t) I 2xi Y: Y. increases corresponds to the rate wit11 @ich the description of the system changes from Yz to Yk. .. A similar set of equa. 41' might be zero except during the period t. Zn.2). the last term will not contribute initially. .27) becomes Substituting the value of X ' in the expression (3. The time-dependent perturbation of the . system comes under the perturbing influence of the field of the electro- magnetic radiation. t ) = Z an(t) Y ~ ( x. . Zn.. . . a' becomes Multiplying thro:~ghoutby Y z and integrating over the entire configuration space... tip electric vector of the incident radiation induces a dipole moment er in the molecule along its direction (Sec. e rate with which the coefficient a.23). &cillating electric field of the radiation disturbs the potential energy of tions can be written for any other time t". the x-component of the displacement for the jth particle of the system. and we have The wave function satisfying this equation is a function of time and the coordinates of the system. El. 1f we consider the simple case consisting of only two states n and m then turbing term 41' may be a function of time as well as the coordinates of on expanding the system. En. a. When the time variation of the field is introduced (Section 2. Y(tl) is a func- tion of coordinates only. Y>re wave functions of stationary All ternns on the left vanish except that for n = m due to orthogonality states corresponding to the energy values E. 3. This change can be represented by the additional term 41' in the Harniltonian of the unperturbed system. . When the property of wave functions and from the conditions of normalization.7 (t) IYi 41' Y i Y. This is a set of simultaneous differential equations in the function am(t). The unperturbed Hamiltonian Sois independent of t.. whereas the per. Y(x Zn. Therefore. The general solution can be represented as Y(xl. . . The expression X cl x j is known as the component of the On simplifying and rearranging (3. . For example. will have different values.nr (3 30) Since initially the system is in the lower energy state n. t ' ) This equation gives the rate at which a system changes from one stationary n @tie to another under the perturbing influence of the radiation.26). Zn.. 2') = C any: (XI. Schrodinger equation is given as dam 7= .. When the oscillating electric field of the electromagnetic radiation in equation (3. say t'. . The perturbation energy along the x-axis as given by the perturbing Hamiltonian 41' is *re Ex is the electric field strength in x-direction and ej represents the ebarge and xj.. we get interacts with the molecules composed of positive and negative charges. In general. we have electric dipole moment of the system along the x-axis and is represented by Fz.24) ?n it. the potential energy of the system changes due to the interaction. we must find out the nature of perturbation The quantities an(t) arc functions of t alone such as to cause Y to satisfy &pposed on a system of molecules when the electromagnetic radiation falls the Schrodinger equation for the perturbed system. Substituting (3.

+ ..En .hv) t 211 E m -En + hv +I-eh .39 -00 X where I pxnmI = $ Tm9Zej XI+: d~ is known as the x-cornpones of the + Let x = K (Em. the first denominator approximates to zero.E n . expression. For a single frequency the term pxnm( E. This where E2(v. transition moment integral or responding to the transition n -t m. a range of frequencies i s involved.~n . . corresponding to light absorption. This is just the Bohr's frequency The rate of change of probability or the transition probability per unit relationship.34) becomes ti' L lf) am(t) = 4 1 Pxnm + ( E- ~En.EZ = E:) the limits .En)/h.e. Since under experimental conditions.36) i &ding the relationship.En.38) -00 This is justified as the effects of light of different frequencies art: additlve and the integrand will he large over only a small region where the deno- $&ator is small.we have 1-eh .(t) and for a single frequency we obtein is given by Bnmp (v. in the region of v near vnm. however. X $in2k(Em .E n . neglecting the first term.am(0)= 0.En .hv) t Ym= +%e '11~~ h t r expression (3.58 FZTNDAMENTALS OF PHOTOCHEMISTRY $ W A N I S M OF ABSORPTION OF RADIATION 59 Separating the space and the time dependent parts (equation 3.h ) t 2'li(~m Em .hv) t ] (Em = --11 E: lpxnml[ P T (3.)' dv (3.hvj2 (3.37) where the imaginary exponentiai is replaced by the sine function. we can write E! (V + dv) for E: (v)t and integrate the expression over For isotropic radiation (Ei .19).hv 1 (3. the molecule (or atom) will absorb a quantum in unit time under unit Therefore. When Em< En.En . respectively. If probability of transition to the state m in time t becomes proportional Em> En.) So we find that due to the presence of the socalled resonance denominator (Em-En . the relationship between the field strength Ex in x-direction sin2 {E (Em.En + hv) t C-i.A.. viz.En .) out of the integral. 7 sin2 x -x2 dx = n. (Here Emand En signify energies of the final and initial states. the second denominator tends B t- -- to zero for the condition hv Em. Taking the constant (v.En 4. the probability that the condition of Bohr's frequency rule.hv) the coefficient am(t)of the final energy state will have a large value only under Now we can introduce the energy density P (vnm) to transform this result into the Einstein coefficient of absorption.). corresponding to light emission (induced) time is given by. i.hv) t and the radiation density is deduced as follows: a: ( t ) am(t) = 4 1 pxnm 1' Er (v) (Em .co to a. On nt sin2 x integration of the expression (3.35) and obtaining the integration constant a: (I) atn (t) = 4 / ~ x m 1'n (VI) p dx from the condition that when t = 0. the probability of absorption per unit radiation density. includes only the term due to a single frequency.(Em . the small and the expression is small unless the denominator is also small.) is the average value of the square of the field strength. (v) is always I hlia seen that as a result of integration over a range of frequencies.hv) t and dx = nt dv so that on substitution.. 25ri 211 (Em . The probability of absorption in the Einstein expression time is given by the product a: (t)a. we obtain Of the two terms in this equation only one is important a t any one time and that also only when frequency happens to lie close to v = (Em. Under tt: influence of the radiation polarized in x-directions.

CI (1.(2E: (vnm) cos 2 n d ) " (3.B m n vnm c3 where c is the velocity of light. when a beam of radiation The square of the transition moment integral ) MmnrZ.dI B m N' hv p (vm) 5 (3. the fractional dsrease in intensity on passage through the solution of molar concentration C and layer thickness 2x and E c (vnm) = - 3 P (vnnl) (3... Therefore.-. If there are N' molecules per cm3. k terms of wavenumbers. Hence a. and I = transmitted intensity. for an isotropic radiation of unit time per unit concentration per unit length of the optical path. When the radiation of frequency (v) is incident on an absorbing system of atoms or molecules. Looking at the problem at the molecular level.) I is the proportionality constant and is a function of incident frequency b n integration over the path length 1the expression becomes {: ln 2 = a. giving ~ambert-Beerlaw (Section 1 .av 2.avCdl (1. can be the sum of the square of the components in x.41): I 4x2 Probability of transition = . y sod z directions: Qkpressed as . I Mnm I' =[ d m n + p:mn i &n] (3.and if the pro- hbility of absorption per unit time per unit radiation density is given by &.1) Substituting for E:'(v.44) 4x Experimental determination of intensicy of absorption is based on The average value of cost 2 x v t = 3. By completely analogous treatment in which values of an(0)==0 and a.46) dl can be expressed as : I/ . at Similar expressions are obtained for the contponent of the transitiorl moment 1. $f density P (vnm) passes through a solution of path length dl. When frequency vnm the transition probability is given as tonverted into decadic logarithm ev = . expresses the probability of absorption per integral in y and z directions..dI . the absorption of each quantum of radiation of frequency vnm removes an amount of energy hv. x.. optical density CI F o a~range of frequencies. then the decrease in intensity per unit time. I).I pxnml2 h 2x p (v.2) where I. from the radiation.5 CORRELATION WITII EXPERIMENTAL QUANTITIES = . llnm= B m n as required and Ex h v i n A m .57) ..(0)= 1 . a vector quantity is . 1 (Figure 1.) in (3. are used. the Einstein coefficient for induced emission Bmnis found to be given by the equation: v om vnm =molar integrated intensity over the absorption band. PECHANISM OF ABSORPTION OF RADIATION 61 60 FUNDAMENTALS OF PHOTOCHBMISTRY Hence.53) 5 3.303 = Brim P (vnm) (from Einstein's equation) Comparing we have.= incident intensity at I = 0.. = -.2) which is repeated here for convenience.

The total area under the curve gives the integrated absorption Since I. in the harmonic oscillator problem. Expressing in terms of concentration C mol litre-l. we have.. If the assumption is madrthat Thus the integrated absorption i&tensityis found to depend on the square the optical electron.6 INTENSITY OF ELECTRONIC TRANSITIONS For a range of frequencies 3. r..v &te is expressed as Substituting for Brim from equation (3.1 Theoretical Absorption Intensity The intensity of absorption for an electronic transition is the probability of absorption between two given energy states. between the ground and the first excited if the average frequency v is considered as the band maximum. and +.61) in terms of wave number. IM. the intensity of absorption is measured i n a spectro- photometer for a range of suitable wavelengths. I = ~ ( v n m )c and . i.. is the dipole moment operator (= er). (a) Plot of molar extinction coefficient c . the electron which is excited to the higher energy of the transition moment integral defined as State.66) value at each wavelength is plotted as a function of wavenumber . = (a/Xjl/4 e-ara/% (3. N' N x 1000. where prim is the operator for transition moment. Therefore 3.49) and rearranging.65) Experimentally. at 'ma.I= I+. dl= Bnm N' hvnm (f ) d l Area Im. are the wave functions for the two combining states and I M l2 .pmIndr -m (3.5 Absorption curve. where A i is the half band width. 1000 c Comparing with Beer's law expression (3. v s i . Nlivnm =Bnm - 2303 c b d A . is attracted to the centre of the molecule with a Hooke's law type +m of force.63) Substituting the values for +. the harmonic oscillator wave functions can be used to evaluate h I Ma1 I.6. for integrated absorption intensity A.5a). 8x3 Nhv where 4.e.54) Figure 3. d v and Einstein's coefficient of absorption can be calculated velocity of light: Jter expressing (3.Bnm . q. . N h v n m cdl .-. JIIsCHANISM OF ABSORPTION OF RADIATION 63 !? (Figure 3.. it is related to the radiation density p(vnm) by the factor c.. the illtensity of radiation 'is the energy flux per unit area per unit time. The molar extinction = (a/x)'14 vfTa r e-wafi (3. The transition moment integral M. and 4. respectively. It can be theoretically computed by using the expression for the transition moment integral. C = - dl --. the I ~ e n s i t y .

~ C H A N I S M OF ABSORPTION OF RADIATION 65 64 FUNDAMENTALS OF PHOTOCHEMISrRY the component of the transition moment integral in the x-direction is. -J e j d . = 8n3 = Nxe2 $ p r e M is molecular weight of the substance.iiy: transition moment integral. is known as totally allowed transition. TWO ENERGY STATES 3. d i . the interaction of electromagnqtic radiation with The strength of an electronic transition is generally expressed in terms matter leads to absorption only if a dipole moment is created as a result of a quantity called oscillator strength f. Some are forbidden which can become allowed under certain conditions and then appear as weak absorption For a one-electron transition the ideal value of unity is obtained when bands. This numerical vaiue for the integrared intensity OF absorption is expected when all the N molecules are transferred to the higher energy state. d %=~ Brim . 5 (3. / is known as tbe and has the same meaning as .31xlU' ~xpressedin terms of oscillator strength f or integrated molar extinction 1q. including the continuum. experimental transition probability to that of the ideal case of a harmonic This may be stated symbolically as dp/dt is positive and d2p/dta# 0.-- 23u)c 1 It S03c 2303mc2 (3.2 Strengtb of an Electronic Transition-Oscillator Strength As already discussed. A transition with f = 1.67) D = ( M n m I* or I R n m l2 = ePQ2 (3. The oscillator strength can also be obtained from a comparison between the number of lines theoretically expressed as . vibrational or rotational (3. But the transitions between all the electronic. During the process of emission the dipole is destroyed..e.69) tive index.c Hence. For atomic energy levels..7. e -. that is The strength or intensity of absorption is related to the dipole strength [ j e j d i 2X ~ : . n the refrac- I6. each absorbing a quantum of radiation.74) a= h v c (prod= reduced mass = m 4n2pxed for electron) The concept of oscillator strength was developed from the classical J . and is - f= [IEGdd] ideal 2. The rules which govern such transitions are known as selection all the molecules are transferred to the higher energy state.1 The Basis of Selection Rules 3. gkhme.6.70) states are not equally permitted. It is related to the molar refraction R of a substance h =-. J the density.P =/ir + wary of dispersion. - Nk v. 1" + (l / Pair P I P0l. when the rules.73) Substituting for d 2a . The summation is over all the blnds or energy states to which the transition can take place from the ground state ri. i..3e2-. r h d~ = dipole length (3.7 THE RULES GOVERNING THE TRANSITION BETWEEN standard for expression of actual absorption intensities. oscillator. :@@olestrength of transition . I 1 hrx = I (a/x)lI4 e-ax" ( e x ) (a/n)lI4 4 5 x e-ax"2 iix jw t r r xl2element is sometimes written as 1 R n m 12. 3 Q= I 4.68) t'r 8xZmvc 8x2m .. --. I=. of transition D or square of the transition moment integral / M. There are a few other related quantities .&hich are used for expressing the strength of an electronic transition. of the electric dipole moment where 1 R. This value is considered as a reference 3. It is defined as the ratio of the of such interaction.- 3o2h (3. these selection rules have been empirically transition probability is unity. v the frequency of the radiation field and fmn the oscillator $brength for transitions between the states n and m which absorbs a ktquency corresponding to vnm. ~ I Mo.

to 0 and 0 to moment can be written as + a.x. For convenience. When the atom reverts to its original energy state p 4 s. are alternatively symmetric (S) and antisymmetric ..6. Such transitions have very low probabilities.76) two parts : . the dipole momeilt vector allowed between a g state and an u state only. a dipolar radiation can bring about changes only from s 4 p . a quadrupole radiation is (A) (B) required since two nodal planes have to be created by the incident radia- Figure 3 . g -I+ g (forbidden) and are applicable for systems Let us consider two types of possible transitions. by pictorial ~epresentation of s and p one-electron orbital functions These observations can be further generalized. f . If the radiation is of a frequency in resonance with the transition 1s + 2p... That is += /Mnml =[I IL: -a jnrn~dr]'#0 (3. an odd function changes sign on changing the establishing the selection rule A1 = 1. transition. Thus. 4 1 = . There is no such restriction imposed Tbr n. To understand the selection rules we have to consider the symmetry properties of the three functions 1m n 1= C (ex) (m dx +n (ex) (tn dx (3 . i0. The transition is alw~ysodd since it changes sign at ths origin. 2 . These two statements are symbolically written functions are either odd (-) or even (+). . the radiation is absorbed. sity of electric quadnipole component in the radiation field is only 5 x lo4 of that of the dipole component. and the change in angular momentum quantum number A 1 = 1 in each case. Also 1s -t 2s. - +1 h where y. in terms of odd and even character. +a The same conclusions can be drawn from the quantum mechanical condition that the square of the transition moment integral I M n m l2 must + jl (+)(+I (+) + J (+)(+) (-) +x = (+) + (-) + (+) -+ (-)=O: be nonzero for a transition to be induced by electromagnetic radiation. combines with an odd function p. the integral can be further subdivided for the problem can be obtained if we consider one electron wave functions point by point multiplication of odd and even functions. 6 Graphical integration of transition moment for Is + 2s and Is a 2 p transition to emphasize the selection rule: I MI # 0 for an allowed tion field. When a plane polarized radiation with the electric vector directed alo& z-axis is imposed on a hydrogen atom in its ground state ( I = O).6). g -+ u (allowed). & and (. For an s -t d transition. it also says that a transition coordinate from x to . The expression for transition \ . we divide the configuration space into hnctions s. With a centre of symmetry. A qualitative picture of -w 0 With reference to Figure 3. since the inten.1. It is observed to be located with the nucleus as the centre and work out the symmetry of that a nonzero value of transition moment is obtained only when an even each function.a. respectively. the radiation distorts the molecule in z direction such that an oscillating dipole is necessarily created as shown diagrammatically in Figure 3 . or 2p 4 3p transitions are forbidden.. 1s -+ 2s and I r + 2p. Each transition involves the creation of a node at right angles to the direction of polarization of the electric vector. as no transition moment is created or destroyed conforming (A 1 +s I Mnmr I = I +: +a -a (ex) 4% dx -= -X J -a (+I(-)(-)+ o J (+)(-)(+I -x to the selection rule A 1 ... The one electron wave 8 + g is forbidden. With this criterion. The rules so derived state: Am = 0.66 FUNDAMENTALS OF PHOTOCHEMISTRY MECHANISM OF ABSORPTION OF RADIATION expected in the spectrum of (I glven atom and those experimentally obtained (vide Section 2. The atomic wave (Figure 3. within the limits of integration.6). These selection rules can be justified from the mechanics of interaction bet^ ten matter and radiation. d . For a one-dimensional atomic wave function s. Besides case in the x direction. p. is the dipole moment operator. etc. f 1 and 41 = & 1 whex m anti I are magnetic and orbital angular momentum quantum numbers. or p 4 d or d 4 f . 77 ) +.

10-6 to 1 0 4 f. 3p. Transitions between requirements and dictates that during w e/ec~onic transition.78) band and replace the integral by em.S. The nuclear motion or the electron spins are not affected.*1G4. f = 0 001. = A found to be unity. total spin ideal singlet and triplet states are strictly forbidden.68 FUNDAMENTALS OF PHOTOC-Y W H A N I S N OF ABSORPTION OF RADIATION 69 (A) with respect to the operation of inversion about the origin of the angular momentum must be conserved.01. A.A. = S each of the factors which cause deviation from the selection rules. The rule governing the transition between the states of like multiplicities is most stringently obeyed. .A. 10-I to For molecules.80) For very intense transitions as observed for the dye moleci~les. Hence - f=4. since S. states. Since the two spin functions and system. the molar absorption coefficient at the band maximum. transitions are in the expression for transition moment is symmetric for eiectric dipole forbidden.* lo2. The electric quadrupole operator is tions are the same. we get correlation is valid if we assume a Lorenzian . is dr.= O .= forbiddenness due to symmetry consideration (orbitally forbidden). The half-band-width is defined as the width of the absorption band (in cm-') where the value of E=$ eIDax. allowed transition: 1s + 2p. The factoriza- tion is possible because only tbe electronic functions are involved in the creation of transition dipole (Born-Oppenheimer approximation). = S Tbe observed oscillator strength for any given transition is seldom 1s -t 3d. 4p is allowed.31 x 10-9 Emax A V (3. The electric dipole operator is antisymmetric (A) with respect to p are orthogonal. unless some perturbing influences bring about spin-orbital radiation and antisymmetric for electric quadrupole radiation. 5d is allowed. totally allowed.A. since A. em. ~ 1 0 5 f. the integral has a nonzero value only if both the func- inversion at a point of symmetry. f 1 : allowed changes in the component of the total (odd-even functions). where A. is the half-band-width of the absorption band (Figure 3. A transition is allowed if the product function sjnglet-sit~glet. The spin conservation rule is the most stringent of (1) Spin-orbital interaction. . 1s + 3d. there is often a fairly good correlation between f If in the total wave function (+). of absorption $ e. A certain degree of 'forbiddenness' is introduced for 3d -t 4f. 6f is allowed. 48-2 to 104 3. shape for the absorption 41= +I Xt St (3. = A the product of factors which reduce the value from that of a completely For electric quadrupole radiation..7. = 1.A. =fS =f. = A f=fmfofsfp. that we get f = 1 and the transition is axis.A. 4p is forbidden. 5f. Av. I .7. ~ouplingand thereby change the 'pure singlet' character of the energy For electric dipole radiation. e. one electron orbital (4) is factored and ern.4. The singlet-triplet.5b). since S. fm = forbiddenness due to spin multiplicity rule. 10-l to 10-2 orbital angular momentum in the direction of the molecular Only when f m =f. 5f.A.or triplet-triplet states. 4d. 5d is forbidden.1) The third integral designates the spin conservation rule. 6f is forbidden. This out from the vibrational function ( X ) and the spin function (S).A. The second expression gives the overlap requirement of the molecular vibrational eigeofunctions and is a quantum mechanical expression of the 3. The first integral Thus for f = l . the rules governing the transition between two given f. drv and dt. But such transitions . vibrational m d 2000 cm-l which predicts spin functions.A.3 Modification of Selection Rules Franck-Condon principle (Section 4.2 Selection Roles for Molecular Trapsitions f. d t .. = forbiddenness due to overlap criterion. = forbiddenness due to parity consideration energy states arc (i) A A =0.A. 4d. The oscillator strength of a given transition can be conveniently cxpressed as 2p -t 4f. = S where. As a consequence allowed transitions are only between inversion symmetric (S). are the configuration space for electronic. since S. 1s +Zp. f=0. since S. (ii) A S = 0 : the spin conservation rule. Although oscillator strength is proportional to the integrated intensity (iii) Symmetry properties of the energy states must be conserved. since S.A.S.. assumed to be independent of each other. and so on. e m a . is the electronic transition moment which has already been discussed. emuel@. 3p.

Benjamin.82) and (3.85) Figure 3. dr (forbidden) +A I Y.70 FUNDAMENTALS OF PHOTOCHEMISTRY &&ANISM OF ABSORPTION OF RADIATION do occur under the influence of intramolecular and intermolecular per. is expressed as A linear correlation with the atomic number Z.A.H. (3. ~ T (allowed) (3. ( ~ f t e rR. is the interaction energy which flips the electronic spin. where 0 is the angle between the two vectors) and K is a Iodine constant for the molecule. and ISo -t SP.S ) (3. Linear relation between atomic number Z and For the singlet ground state. The Hamiltonian operator which causes the mixing of states of unlike multiplicities is Carbon expressed as Nitrogen A. and pure singlet Y. the first term is zero but the second term ratio of intensities ISo -+ IP. under spin-orbital coupling interaction the transition moment IMI for transition from singlet ground state to a mixed ~ r r i t ~~dt a t eis given as = I Y$Y. (L *S)is the Chlorine scalar product of orbital and spin angular momentum vectors respectively Bromine ( L * S = a cos 0. 1964) expression (3. . From York: W . The S -+ T transition is said to borrow intensity from S -+ S transition. Hocstrasser.1 turbations which can mix pure singlet and pure triplet states. Es and ET are the energies of the singlet and triplet states respectively. smaller is the energy gap between singlet and triplet states. The wave function obtained on such spin-orbit Lead coupling interactions which cause mixing of the pure triplet Y. Behaviour of Electrons in Atoms. Thus. the larger is the mixing coefficient A. The heavy atom Hg has consider- where A indicates the degree of mixing and is given by able intensity for intercombination transitions. transitions in Gr I1 atoms. The values for several cular oxygen has a perturbing effect on S . The and is seen to be directly related to and inversely to the energy separation dramatic enhancement of S . The transition intensity is proportional to A. These Values of E for atoms obtained from spectral data perturbations are functions of the magnetic field near the nucleus and are Atom therefore a function of atomic mass (heavy atom effect). for lS + SP1transition in Y ~ ~ = Y > +AY.= K S ( L . Y . Mole- close to the nucleus of a heavy atom such as iodine.T absorption spectra of organic atoms have been calculated from atomic spectral data and are presented molecules in solution.T transition due to intramolecular and between the singlet and triplet states. Therefore. TABLE 3. Vsowill be large also if the molecule is paramagnetic. ~ l a t o m i numbers! c Spin-orbit coupling.7.84) The effect is observed when the heavy atom is substituted in the molecule (intramolecular effect) as also when the molecule collides with a heavy atom containing perturber (intermolecular or external effect).well defined in the Table 3 . E is a function of the potential intermolecular heavy atom perturbations are respectively shown in Figure field near a nucleus and has a high value for an orbital which can penetrate 3.82) Oxygen where E is a function which depends on the field of the nucleus. . Under a pressure of 100 atm of 02..83) Gr I1 atoms is illustrated in Figure 3. l .7 l o ~ . and V.8 for chloronaphthalenes in ethyl iodide and other perturbants. New contributes.

FUNDAMENTALS OF PHOTOCHeMISTRY MECHANISM OF ABSORPTION 0 3 R A ~ I A T I ~ N 73
s - T absorption spectra are obtained for aromatics, heterocyclics, olefines
and acetylenes. The transition disappears on removal of oxygen. It is
- 0
m
suggested that a charge-transfer complex (A+ 0;)(Section 3.10.1) is
formed which relaxes the spin multiplicity restrictions.
- QI
c-u ~0 'a 2c ; (ii) Symmetry forbidden transitions-vibronic interactions. It can be shown
a P,O
$s2 from group theoretical considerations (Section 3.8) that a n -+ x* transition
- ID
0'8 in formaldehyde should not occur. It is overlap forbidden since non-
e, Sa bonding orbitals on 0-atom are directed perpendicular to the plane of x*
2a -b 2- 22 antibonding orbital in C = O group (Figure 3.9). In pyridine, the lone
:- $ 0 . 0
- * YE m 22 4 pair on nitrogen occupies an sp2 hybrid orbital and because of the
N U 0 rr
;; ~ C S s-character, such a transition gains in intensity (Figure 3.9). When such
transitions do occur though with very low intensity, they are said to be
- N induced by unsynmetrical molecular vibrations.
- i e
h O
~ M-I' + < ( C x , z)CIEdr
- 0 2;s -m
(Y

-Ed E i
- 2
2s-
2 c ..
- n +'n on Iza - NITROGEN
2:;
1 1 1 1 1 1 - .
2 3$
0 ~ 0 0
.5 e;;;l "* 1

n - .2 a
.= .g 2
VI
g, -
0 0
-
c.0
2-.c
X-

st E
g
c m
.....

W
%z.
C
n 4 n* on catbonyl- OXYGEN

5 .z a
3. ei
- .9
, , c
c h; 9
8 - .. . . .
t
+
Figure 3.9 Schematic represe~~tationof transitioll moment integral i n , pyridine
and formaldehyde. (Ref. 3.4).

00 A different kind of symmetry restriction is the cause of the small
m intensity of 260 nm absorption in benzene ('B,,clA,,). T3e electric
e dipole moment vector of the electromagnetic radiation cannot generate 'B,,
.-z
0
N
0
0
N s0 o
0
o
0
CL form of excited state from the totally symmetric' hexagonal ground state
0
designated as 'A,, (Figure 2.19). The restriction of the symmetry selection
Ai~suaple31idO rule can be broken down by vibration-electronic (vibronic) interactions. The
molecular vibration which can change the molecular symmetry for 260 nm
transition in benzene is designated as E,,.

74 FUNDAMENTALS OF PIIOTOCAEMISTRY lblgCHANlSM OF ABSORPTION OF RADIATION

3.7.4 Group Theoretical Approach to the Selection llules
If we draw an arrow to the coordinate axes to which the symmetry of a given
molecule is referred, then the transformation properties of these translation vectors
under the symmetry operation of tbe group are the same as the electric dipole moment
vector induced in the molecule by absorption of light (Figure 3.10).

-,
0.

(0, 1 la, 1

Figure 3.11 Symmetry and charge distribution In molecular orbitals of
formaldehyde: n (b2), n (bl) and n* (b,) and a* (al).
Translattm almg Zaxds Rotatrm about Z3x14

Figure 3.10 Transformation properlies of translational and rotational vectors. similarly, n* and a* transform as the symmetry species b1 and al respectively.
The electronic configuration of formaldehyde under different types of electronic
The induced magnetic dipole moment has transformation properties similar to transitions can be represented in terms of electron occupancy (Table 3.2). To obtain
rotations R,, R,,, and R, about the coordinate axes. These transformations are the molecular state symmetry the symmetry of singly occupied orbitals need only be
important in deducing the intensity of electronic transitions (selection rules) and the considered for the direct product (Section 2.9).
optical rotatory strength of electronic transitions respectively. If P and R are the
probabilities of electric and magnetic transitions respectively, then
TABLE 3.2
The energy state, electronic configuration, molecular state symmetry
and the nature of transition in formaldehyde molecule
-
Energy Electronic Molecular state Selection rule for polariza-
where +,
.
and 6, are wave functions for the ground and the excited states respectivel)
and Ex,, ,and H z , ,, are the sum of electric dipole operators and magnetic dipole
operators, respectively, in x, Y , z directions. The probability of transition is nonzero
state configuration symmetry tion of transition dipole

only when the integrand is symmetric with respect to all symmetry operations since
an antisymmetric integrand gives a zero value for integration between minus infinity
sm7* 02n4nlX*1 b2 x bl= A2 overlap forbidden
and plus infinity Thus, to establish whether an electronic transition is allowed s7,* ~2~ln2n*l b, x b,= 4, z-polarized transition
between two energy states. it is sufficient to show that the complete integrand be- Sm* 02n2nla*l b2x a l e B2 y-polarized transition
longs to totally symmetric species. Let us take the forma!dehyde molecule for an
example.
The state symmetries of formaldehyde can easily be deduced from group theoretl- Once the state symmetries have been established it only remains to be shown that the
cal considerations. The wave functions of n, 12 and x* orbitals are pictorially direct product of the species of the ground state symmetry, thecoordinate translational
represented in Figurz 3 . l l with coordinate axes as used for the molecule. SYmmetries and the excited state symmetry belong to the totally symmetric species A,.
Like water, it has the symmetry of point group Cz, When the MOs of for- Let Us take the n+r* transition in formaldehyde. The ground state total wave
maldehyde molecule as given in the figure are subjected to the symmetry operations function has the symmetry A,. The coordinate vectors x, y and z transform as B,,
of this group, x-orbital is observed to transform as b1 and n orbital as b2 as shown 4 and A, respectively (refer Character Table for C2, ; Section 2.9, Table 2.2), The
below : excited state transforms as symmetry species A2. The direct products are:
E(x) = = + 1 ( ~ ) E(n) = + l ( n )
C2(n) =-1 (x) C(n) 0 - l ( n ) -for x-polarized transition, Al x Bl x A2=B2 forbidden
+
O? ( x b 1 (n) G? (n)= - 1(n) for y-polarized transition, A l x B z x A2= Bl forbidden
o r (n)=- 1 (x) 0:' (n)= 4- 1 (n) for z-polarized transition, A, x A, x Al-Aa forbidden
hence n transforms as bl hence n transforms as b2

OF ABSORmON OP RADIATION
~ECHAN~SM

and establish that n+r* transitions are forbidden from symmetry considerations. On
the other hand, n+o* promotion is allowed for y-polarized incident radiation of
proper frequency. This excited state transforms as symmetry species B2. Therefore.
for X-polarized transition, A, x B, x Bz= Aa forbidden
for y-polarized transition, A, x B2 x Ba=Al allowed
for z-polarized transition, A, x A,x Ba=Ba forbidden
The same predictions can be read directly from the character table from the pro-
perties of translation vector.
The n+n* transitions of aldehydes, although forbidden from symmetry considera-
tions may be allowed through vibration-electronic interactions and, if allowed, are
always polarized out-of-plane (along the x axis). The transitions of (r+r*) type are
polarized in-plane along y or z axis. These characteristic polarizations lead to
differences in physical interactions between molecules. The optical rotatory strength
which contributes to the optical rotatory dispersion of an electronic transition is
given by a scalar product of two different vector integrals (equation 3.88). The
first integral is the transition moment integral and the second integral involves the
magnetic moment operators which have the symmetry properties of rotation R,, R,
and R,. The translations T,, T, and T, and the rotations R ., R, and R, transform
in a complementary manner. If the molecule has a plane of symmetry or a centre of
inversion, the product of the two integrals may be zero. This explains the fact that
optical activity can be observed only for asymmetric molecules, with no plane or
centre of symmetry (inversion).

3.8 DIRECTIONAL NATURE OF LIGHT ABSORPTION Figure 3.12 Directional nature of light absorption in Hz molecule.
Since the electric vector of the incident radiation is responsible for the V d o r perpendicular to the molecular axis, the charge density can only change in a
creation of a dipole moment during the act of absorption, a difference in perpendicular direction with the nodal plane along the molecular axis. The transi-
the strength of absorption is expected for different orientations of an- tion is to xu state if the choice of frequency v, is correct. It is assumed that the
,molecule is fixed in its orientation.
isotropic molecule. The absorption spectra as obtained with ordinary
light do not give this information. For the determination of the direction Example 2
of polarization of the oscillator, absorption spectra need to be obtained
Anthracene absorbs a t two wavelengths, at 360 nm and at 260 nm. The flat
with polarized radiation in rigid systems of' properly oriented molecules such molecule is anisotropic and it has long axis along x coordinates and a short axis
,IS crystals. The directional nature of light absorption can be explained along y coordinate. The absorption at 360 nm is short axis polarized (Latype). A
from the considerations of symmetry properties of the energy levels involved substituent at 9, 10 or 1, 4, 5, and 8 positions may help c r retard the creation of
in the transition. It is best understood by discussing few specific examdes. dipole in this direction. Therefore, the intensity or position of this absorption
region may be influenced by such substitutions. The absorption at 260 nm is long
axis polarized ( L b type) and is perturbed by substitution at 2, 3, 6 and 7 positions.
Excmple 1 Such substituent effects are sometimes used to identify the polarization directions of
Let us consider the sirnolest molecule Hz. In the ground state the two electrons a given electronic transition.
occupy the lowest energy level of symmetry .z : Since the molecule is anisotropic
two possibilities arise-if we use a plane polarized light, the electric vector of the light The polarization directions for transition in some pyrimidine molecules
is either parallel to the molecular axis or it is perpendicular to it (Figure 3.12). In are illustrated in Figure 3.13.
each case, the dipole direction will be along the direction of the electric vector (e v)
and a new node will be formed at right angles to the e v. The symmetry of the two
lowest excited states of Hz-molecule corresponds to 2, and T, respectively. When 3.9 LIFETIMES OF EXCITED ELECTRONIC STATES OF
the incident radiation is polarized parallel to the molecular axis, the transition dipole ATOMS AND MOLECULES
created is also in the parallel direction with the nodal plane perpendicular to it. If
the frequency of radiation v, is correctly chosen, an electron will be promoted from When once an electron is raised to the higher energy state by absorp-
P, to 8,. On the other hand, when the plane of polarization directs the electric tion of a quantum of radiation, the question naturally arises as to how

95) is known as the natural radiative lifetime of the atom or molecule. N long it will remain in the excited state before returning to the stable ground state.:mf this time the system spontaneously reverts to its origiqal state by emission of radiation of appropriate energy. The expression (3.r. gm = 1. respec- If k = 117 then I = I. The theoretical basis for the empirical mirror symmetry relation between fluorescence and absorption spectra for large molecules depends on the approximate parallel nature of the potential energy surfaces of ground and excited states of molecules such as dyes where bond lengths are little affected because of delocalization of the electronic energy.14 Decay curve for omision intensity and the definition of lifetime .13 Polarization direction for transition in some pyrimidines. Thus the natural radiative lifetime TN is inversely mlated to the rate constant for the spon- < where is the wave number of the approximate mirror image reflection plane of absorption and fluorescence spectra plotted as function of . The natural radiative lifetime gives an upper limit to the lifetime of Tim --P an excited molecule and can be calculated from the integrated absorption Figure 3. to deca. For singlet c singlet transition.95) is truly applicable to atomic transitions only but it gives fairly good results for molecular cases also. Therefore the lifetime is defined as /he time fakenfor the radiation intensity A more refined expression is given by Firster. The time an electronically excited electron spends in the higher 3.7). useful for intercombinatio~ constant for the emission process and has the dimension of reciprocal transition between a singlet and a triplet state. A spin statis tical factor should be included for intercombinational transitions. at zero time and at any time t after the exciting radiation is cut off.61) - k = 8x v2mar C.5 energy states of an atom or a molecule.47 x 108 1 1. (3.93) Figure 3. From equation 3. spin statistical factors for the upper and the lower energy states.96) is used and . from (3.(section 5. for triplet c and for a time t = ~ singlet transition gm = 3. Here gm and gn are the time.98 PUN~WENTM OP PHOTOCH~MBTRY &XIANISM OF ABSORPTION OF RADIATION ?!3 -us emission process. After . and gn = 1. the rate of decay follows a first order rate law and can be fifractive index n. In a system of large number of A more general expression for molecules dissolved in a medium of particla. The quantity to be plotted is €3 vs if (3. is expressed as I = I. The latter is identical with Emstein's spontaneous d s s i o n probability Amn from all the upper energy states of the system to the ground energy state. Such relationship may not exist for small molecules. gn = 1 . k is the rate where gm/gnis a multiplicity correction factor.14). respectively. e t P (3 90) tively. (3. (3.~to lie th qf its original value (Figure 3. and Zare intensities of emitted radiation.10 On substitution of the value for Bmn. and ?N = -- . if left unperturbed by the environment.89) where I. intensity.

T n-tn* appropriate regions of the spectrum..1 . the transition polyatomic molecules.9 . S-S n+n* As already discussed (Section 2 ..0 S. such as collisions with the solvent molecules or any other molecules ' perturbation technique is a useful way to identify transitions as n + x* present in the system. The natural radiative lifetime is independent of temperature.. In an with those in hydrocarbon or nonpolar solvents. vs T. inherent lifetime. S-S n+w* that may be present in organic molecules are o. etc.15. the system may lose its electronic excitation energy or x -+ x* for complex molecules.. n -+ o*. if the band shifts towards actual system the average lifetime T is less than the natural radiative the high frequency or shorter wavelength side (blue-shift) then the lifetime TN as obtained from integrated absorption intensity.8 . 0. weak absorption bands imply long lifetimes and strong absorption bands imply short lifetimes. If there is a small red shift. 5.3.80 FUNDAMENTALS OF PHOTOCHEMISTRY ~ C H A N I S M OF ABSORPTION OF RAD~ATION 81 (2 .15 Correlation between oscillator strength f.6 .OO . PeryIenc: 5.0 . n -+ x* and n + x* are normally 2-Iodonaphthalene 2. lo). They appear in the Acetophenone 8.. 3 are recorded some experimental values and compared with those calculated from (3. 8. The value of TN is greater for a forbidden transitioh whose f-number is less than unity.7 . S-S n+z* MOLECULES Fluorescein 4. 3 t Allowed I Experimental and calculated lifetimes for singlet-singlet (S-S) and singlet-triplet F orb~dden ( S .T ) transitions of ( n + n*) and (n -+ n*) type . Any process which tends to compete with orbital promotion types in hydroxylic solvents such as water and ethanol spontaneous emission process reduces the life of an excited state.110 x 10-9 S-S n+n* r and lifetime T for different transition types.. .. 3. Under environmental pertur. x* and a*. lowering the acetone and ~ ~ r i m i d i nise shown in the Table 3. n.96). is equal to 1 and 3 for singlet and triplet transitions. . x -t x * . 6. f = I and from 3. 10 diphenyl anthracene 8. Therefore. S-S x+x* 9. 15. technique is the most convenient. they are arranged as given in the Figure 2.0 .0 .-- . Energy- Anthracene 9.. Photochemists Biacetyl 1. if (3 .10 TYPES OF ELECTRONIC TRANSITIONS IN ORGANIC 9. 5.. 3..IF.4 . respectively. In many transition is probably n --+ x * ..17.0 x 10-3 0. the types of electronic orbitals lhodamine B 6. While comparing bands of different by nonradiative processes. S-Z' z+n* observed in the near UV and visible regions and are most characteristic transitions. Kasha's tests for identification of n -+ x* and x -t x* Iransitions. TABLE 3 . 10 dichloro anthracene 11 .2. r and TN is given in Figure 3.0 .. noniadiative intramolecular dissipation of energy is likely to be x + x * . o -t o*. In Table 3 . S-S n+n* 3.. For fully allowed transitions. More accurate experimental methods are given in Section 10.96. The factor g. The effect of solvents on the n -t x* transition in may occur even in the absence of any outside perturbation. molar extinction coefficient Anthracene 20. but is susceptible to environmental perturbations. S-T n+n* designate them by an arrow from the lower energy state to the upper . Kasha has developed tests described below for distinguishing between these two types of transtitions.7 .)3 rj/./g..5 . of which solvent perturbation A correlation table for f. Solvent bation.0 .97) is used. energy state as n + x * .4-- Compound (Exptl) in s (Calc) in s Transition Figure 3....0 x 10-9 16.0 .1 x 10-3 S-T n+n* wise.

it may be an n + x* transition. This is because of the poor overlap of the wave functions of ground and excited states in n -+ x* transitions. : I--- I: I: T etracyanoelhylene M~xture I : 3 . . I.4. in absorption: lB. is much smaller than that of a n -+ x* transition..'. of the molecule for rl. If a long wavelength absorption band of weak intensity is observed.* 1 I 300 400 800 (r00 TABLE 3. In strongly acid media. 1 .4 Different nomenclatures for several important transitions in polyatomic molecules Davelength (nm) Ethylene Benzene Formaldehyde Figure 3.1 Charge Transfer Transitions Am. pyridine with benzene. Gerrge )imax=165 nm hmru=256 nrn and Wells. Introduction ro Molecular Spectroscopy-Theory and rmax=l .t&i ot ha acceptor. 2.3 In spectroscopic convention. S-tetramethyl- (perimeter model) benzene and tetracyanoethylene..5 and in emission: lB2u -+ l A l g .A. Kasha n -f x* x + n' ". The protonation may increase the excitation \. the upper energy state is written first followed try the lower energy state between which the traneition is taking place. the transition vectors lie in the plane \'. Mulliken state V t N V cN This band arises due to the transition of an electron from the molecule Plat t 1B t 1A 'La + l A with high charge density (donor) to the molecule with low charge density Molecular orbital + azn n* ozn2 ( a d 2 (elg)3 (ezu)l + (alu)2( e d 4 -(acceptor). In the case of cyclic compounds. nrn 292 290.. an n -+ n* band disappears due to proto- nation of the lone pair.1 Group theory lB.4. The intensity of the absorption band of an n -+ n* transition. -Solvent e&ct on n + n* iransition in acetone Solvent : Hexane Chloroform Ethanol Methanol - Water For absorption. 4. the arrow points from left to right.16). 2 .5 287 280 271 When two molecules which are likrly to form loose complexes are Other tests are as given below. The transition occurs from the highest fiild .SX 10' smaxz 1 . [Adapted from Britain. mixed together. 6 10' ~ Experiment.2.tis of the acceptor --- .remotion of an electron to higher unoccupiad orbt.5 277 272 270 266. Academic Press.4. t 1A 'BZU+ l A l .16 Charge transfer band for thecomplex between 1. Comparison of the spectrum of a hydrocarbon analogue of the hetero- atomic molecule: Formaldehyde with ethylene. quinoxaline with naphthalene.1. for the lowest energy transition in benzene at 260 nm. 279. There are significant differences in the polarization directions of absorption and emission spectra for two types of transition.g. . very often a new featureless band appears (Figure 3. e I A .10. . like pyridine.5 letrawethylbenzene energy to an extent that the band may shift far out into the UV region and not be observed. transition. 1olecuiar degenerate orbital of the donor to the lowest empty molecular orh. Other nomenclatures arc given in the Table 3. . -t z* transition but perpendicular to it for n +x* \ ... Solvent efect on n + n* transition in pyrimidine Solvent : Iso octane Ether Acetonitrile Methanol Water 3. 1972. -ANISM OF ABSORPTION OP RADIATION 83 82 FUNDAMENTALS OF PHOTOCHEMISTRY < TABLE 3.. e. even when symmetry allowed.

84 FUNDAMENTALS Or( PHOTOCHEMISTRY CHAN~SMOF ABSORPTION OF RADIATION 85

can occur to give additional charge transfer absorption bands. Schematic donor and the acceptor centres in A units, and ;is the transition energy in
representation of CT (charge transfer) transitions is given in Figure 3.17. .menumbers (cfn-I). The f-numbers can vary over a large range and
' are sensitive to S and d values.
There are two types of donors, x-donors and n-donors. In the
former, the electron available for donation is located in the x-MO of the
faolecule, e.g. aromatic hydrocarbons, alkenes, alkynes. They are said
to form x-complexes. In the second type of donors, a nonbonding
w t r o n is transferred. The examples of n-donors are alcohols, amines,
@en, etc.
-+-o- -9-u-
0 --O--Q--
, There are many types of acceptor molecules. Some of the inorganic
D A / \2+ aJcceptors are halogens, metal halides, Ag+, etc. Of the organic acceptors
compounds as tetracyanoethylene, trinitrobenzeoe and others which
Figuro 3 . 1 7 Schematic representation of CT transition. &ntain highly electronegative substituents are more important. In
F@ansition metal complexes, intramolecular CT transitions may be observed
The molecular complex formed by the interaction of donor and those cases in which an electron is trdnsferred from the ligand to the
acceptor can be considered as a resonance hybrid of two structures : one
a NO-bondstructure (DA) in which the two molecules are bound together
only by van der Waals forces and the other in which an ionic bond exists
between the donor and the acceptor (Di- - A-). The main contribution
s 1 ion. Such CT bands shift to the red when ligands with lower
ron affinity are substituted as in the case of [Co(NH,),XIS+ where X
& a halide ligand of F, CI, Br, and I. The intramolecztlar CT transitions
p u r in derivatives of benzene with a substituent containing n electrons
to the ground state is from the no-bond structure and the wave function
is represented as
$w as carbonyl or amino group. Charge transfer transitions are
,&portant in biological systems.
G a +(DA)
~ J = +
b +(D-~A-) (3.99) i*~
The coefficients a and b describe the contribution of each structure 3.10.2 Ch8racteristics of x -+ TC*,n -+ x* and CT Transition
1%
and for the ground state, a, b.
Io the formation of the excited state, an electron is transferred froin $, Aromatic carbonyl compounds provide examples in which absorption
@ds can be identified as due to x-+ x * , n +x* and CT transitions.
donor to acceptor. A: a consequence the ionic form becomes the 4 rough guideline for identification of a given band due to any of these
predominant contributor in the excited state .arJlllsitions and properties of the corresponding energy states have been
+e = a* $ ( D A ) - h* $ ( n + ~ - ) (3.100) &n in Table 3.5
<
where a* b*.
TABLE 3.5
Since a CT band arises from a transfer of an electron from donor to
Characteristics of the excited states of aromatic carbonyl con~pounds
acceptor, the energy requirement is dictated by the ionization potential,
IP, of the donor and the electron affinity, EA, of the acceptor. It has
been found empirically that the energy of the CT band, IncT,for a series State
of donors and the same acceptor can be expressed as

Transitions
where A is a constant for the related series of donors. Intensity (log r )
The intensity of an S, t- So charge transfer band is given appro xi mat el^
Energy range (cm- 1) 30,000 40,000 30,000
by
(3.102)
Solvent shift (cm-1) -800 +600 + 2300
f = 1 .093 x 10-5sQcL
-
where S is the overlap integral given by S $ ( I , + , &, +n and +,n beil:g
cianor and tcceptor orbitals respectively. d is the distance between the
'r-S splitting (an-I) 3,000 8,003 3,000

m&HANiSM OF ABSORPTION OE RADIATION 87
FUNDAMENTALS OF PHOTOCHEMISTRY
TABLE 3 . 6
(Table 3.5 Contd.) CTTS processes in aqueow solution
-
__.-___ _ - -- --- --- -- --

State
- .-.-
Ion A (nm) Process
-.
C-L-

Triplet lifetime at 7 7 O K (s) <0.02 1- 253.7 1. +,;e
Electron diHribution on C==-0 8 - 84- X- 184.9 X. + t i
>C-0 > c==o (X P CI-, Br-)
Polarization of perpendicular
to the molecular
in the
molecular
perpendicular to
the molecular
OH- 184.9 *OH + :c
transition moment plane
olane plane SO:- 184.9 *SO;+ e,
Reactivity or H-abstraction c O ~ 184.9 *COL+ e;4
1 0.1 0.0
from iso-propanol FC(cN):' 253.7 Fe (cN)~-+ e i
7

F C ~ 253.7 Few +e i

3.10.3 Charge Transfer to Solvent Transitions
The absorption spectra of anions are very sensitive to the composition 3.11 TWO-PHOTON ABSORPTION SPECTROSCOPY
of solvents in which they are embedded. In general, they are solvated,
i.e. they are surrounded by a solvent shell. The molecules composing the The study of short lived excited states is limited by the low concentra-
solvent shell constantly exchange position with those in the bulk of the tions in which they are created on excitation with normal light sources.
solvent. In these transitions, an electron is ejected not into the orbitals The use of high intensity sources such as flash lamps with suitable flashing
of a single molecule, but to a potential well defined by the group of mole- rates and laser sources have been helpful in this respect. Triplet-triplet
cules in the solvation shell. Such transitions are known as charge-transfer- absorption, absorption by excited singlet state to higher singlet state and
to-solvent (CTTS) transitions. absorption by exciplexes (Section 6.6.1) can be effectively observed by
A classic example is the absorption spectra of alkali iodide ions which sequenrial biphotonic processes.
are f ~ u n dto depend on the nature of the solvent but not on the nature The simultaneous absorption of two visible photons in a single transition
of the alkali. The spectra consist of two absorption maxima at energies also be made to occur using high light intensities available from lasers.
529.3 kJ and 618.4 kJ, which closely correspond to the energy difference h ~ - ~ h o t absorption
on spectroscopy is able to identify and assign atomic
of 90.92 kJ, between I (54P,I, - 52PIl2) of I atoms in the gaseous state. and molecular states which are not accessible to the usual one-photon
The steps in the transition process can be represented as follows: absorption. The electric dipole (ED) allowed one-photon absorption has
)4@ transition probability between states of opposite parity g + u, u -+ g
(A1 = f I), but two-photon transition can occur between states of same
Parity g + g, u + u, (A1 = 5 2). The absorption results from two ED
In aqueous solutions, it has been shown that the solvated electron e , hsitions. The quantum picture for two-photon simultaneous process is
circulates in the solvation shell until it is captured by I, to given an 1, that if two photons A and p of frequencies and FP each of which indivi-
radical ion which is finally stabilized to I;. The solvated electrons have dhlly is not in resonance with any of the energy levels of the absorbing
a characteristic absorption band near 700 nm which has been detected in qolecules but are so when combined, can induce free oscillations in the
flash photolytic studies of aqueous KI. The orbital of the excited electro* . molecule. The two photons are destroyed simultaneously and the mole-
may be considered to be spherically symmetric like that of a hydrogen
atom, with its centre coinciding with the centre of the cavity containing
*
is raised to an excited state. If the two photons strike at right angles
b e a c h other, they can overcome the symmetry barrier for the selection
the ion. r ~ k for
s angular momentum for single photon transitions. On the other
Similar CTTS spectra have been observed for Fe(CN):-, aqueous b n d , transitions betwee11 states of opposite parity become disallowed.
solutions of phcnate ions and many other inorganic ions. Some e x a r n ~ ~ ~ ' Thus for naphthalene, the transition (A) is forbidden for single photon
are given in Table 3.6. 3 ~ t r o s c o p yboth for x and.y polarized process, the transition moment.

88 FUNDAMENTALS OF PHOTOCHEMISTRY MECHANISM OF ABSORPTION OF RADIATION 89

integral M = 0. Rut i t becomes allowed for ttvo photo11 procesb (B) as where is the transition moment operator. rt is derived from the Schrbd'ngcr
equation including time by application of time dependent perturbation imposed
shown in Figure 3.18. The nonzero value of transition moment integral by oscillating elcctric field.
indicates allowedness of transition. M,, is transition moment integral for 4. Thc symmetries of thc initial and the final wave functions and of the electro-
g -+ g transition. 6 magnetic radiation operator determine the allowedness or forbiddenness of an
electronic transition. The transition moment integrand must be totally symmetric
for an allowed transition such that I M,, l2#0.
5. A transition may be forbidden due to operation of the law of conservation of
spin momenta AS=O.
AB 6. Spin selection rule can be modified by spin-orbit coupling interactions.
( ground) 7. Symmetry forbidden transition can be made partially allowed by vibronic
interactions.
8. A totally allowed transition has oscillator strength f=l and molar extinction
coefficient -lo5. Different factors may reduce the f values to different extents.
Oscillator strengths f are related to integrated absorption intensities by the
expression

9. The prdbability of absorption givcn by the Einstein coefficient of induced
absorption Bmn can be expressed in terms of ( M (2,

and Einctein'j coeficient for spontaneous emission.

64dv;,,,
A,, = I Xf I ?
:/IC 3

10. Excited state lifetimes are re1at:d to the Einstein coefficients of spontirneous
emission A,, and can be approximately calculated from the expression
Figure 3.18 'Schematic representation of transition moment integral for monn-
pbotonic and biphotonic transitions in naphthalene. (A) Transition
forbidden by one photon process;' (B) Allowed by two photon
process. 11. n + n*, n -+ n* and charge transfer (CT) transitions can be identified by solvent
I M:,, [ = x-polarized monophotonic transition g -+ g
-
I Mi,,l y-polarized monophotonic transition g +=g'
1 M:,I, ] Mz,, I = biphotonic transition, two photons polarized at
perturbation technique and by the shape and intensity of the corresponding
absorption bands.
12. Some solvated anions like I-, Fe (cN$-, phenate, etc. eject an electron into the
right angles to each other. solvation shell on electronic excitation. Such a solvated electron erq, thus gene-
[Adapted from W.H.McClain-Acc. Chem. Res. 7 (1974) 1291 rated, absorbs at -700 nm as observed by flash photolysis.
13. The two-photon absorption spectroscopy can o\ercome the symmetry barrier
Summary imposed by the selection rule for angular momenta in the one-photon process.
1 Electric dipole radiation is the most in,,,ol cant component involved in normal Thus, the technique is able to identify and assign molecular and atomic states
excitation of atoms and molecules. Th: electric dipole operator has the form which arc not accessable to one-photon spectroscopy.
Bejxj where e is the electronic charge in esu and x, is the displacen~entvector
for the jth electron in the oscillating electromagnetic field.
2. The dipole moment induced by the light wave ic a transitory dipole moment
and is not related to the permament dipole moment of the molecule. It is known
as transition moment.
3. The transition moment is measured by the iransition moment integral which for a
transition between the energy states m + n is expressed as

. The quantized vibrational energies are #ven by Physicochemical Properties of the Electronically Excited Molecules Rotatioorl levels v'.1.1 NATURE OF CHANGES ON ELECTRONIC EXCITATION (quanturr numbers V'-0.0 . a double bond to become single and a . pK values.1).. Bond angles may change by as much as 80" because of changes in #here r defines the displacement from the eqliilibrium position r. is expressed as electronic configuration but differing in spin multiplicity. 1 .I". Certain other physical properties like dipole moment. krmonic motion as derived from Hooke's law is given by single bond to disrupt.. Since the charge densities are different it shows a different Rotattonal levels chemistry from the normal ground state molecule. 1.1 Electronic energy levels of mokculas with associated vibrational and the ground state values. Usually the equilibrium internuclear distances increase. leading to direct dissociation E. 3 in their potential energy surfaces. for a simple harmonic osciIlator where v.1. CAL PROPERTIES OF THE ELECTRONICALLY EXCITED MOLRCULBS 91 F g C s in the vibrational envelop and interrsitics.2 ). Excited states... For polyatomic molecules with the same b w n as the force constant. and k is the degree of s-p hybridization.. (quantum numbus ) V~brat~onal levels 4.rP)% (4. more so because it has (quanturr numbers . Bond distances may increase by about 15% or i: V ( r ) = 4 k(r . 3.. 2 ) excess energy but weaker bonds.. the differences in electron-electron repulsion terms in the singlet and triplet states may give rise to different geometry and bonding properties. ..1) on transition to them. \ 1.. have less deep minima rotational levels. EJ. redox potentials also differ in comparison to ~Fipure4.2) more. The potential function V(r) for simple triple bond to become double. the vibrational quantum A transition from a bonding to an antibonding orbital can cause a h m b e r has values 0. A molecule in the electronically excited state can be a comple- tely different chemical species with its own wave function and nuclear geometry. in general.2 . VlBRATIONAL AND ROTATIONAL ENERGIES 5 FOUR 4 ~ a c electronic h energy state is associated with its vibrational and rota- e l energy levels (Figure 4. Some of the states may be completely repulsional. I J'. etc. The rotational energy.0. = (v f) + (4. indicative of the weakening of attractive ti interactions. 2. #J ELECTRONIC. These changes in the geometries are reflected in the respective absorption bands in the form of .

2). For higher vJues of v. But for polyatomic molecules. various v' -+ v" transitions are designated as 0 c 0.3. is equal to the depth of the potential well internuclear distance which is identified with the bond length. 1. The distribution function as obtained from the solution of the Schrodinger equation for various values 4. changes in vibrational and rotational quantum numbers occur giving rise to fine structures in the absorption spectrum. The energy is totally Potential energy curves for a diatomic molecule (Figure 4. Each excited measured from the zero vibrational level. = Do . are commonly kinetic at the centre and totally potential at the turning points.Jhv into 3N-6 components termed normal modes of tibrations (3N--5 for where #hv is known as the zeropoint energy and exists as a consequence of the Heisenberg uncertainty principle (Ax Ap h).2 for each energy state The shapes of the absorption band associated with the intensities of vibra. are sensitive functions of the equilibrium bond length.. in course of oscillation the molecule classically spends most of its time near the turning point. E. the dissociation energy. The total energy Ev is a constant for any given vibrational level but tional transitions. I pys1CAL PROPBRTIES OF THE ELECTRONICALLY EXClTED MOLECULES 93 as for a rigid rotator where J is the angular momentum quantum number and can have values 0. The dissociation energy D.bra- tional structure if such be recognized. bond oscillates about the equilibrium position. It is State has its own characteristic potential energy curve and its own equili- brium internuclear distance.2 Electronic absorption and Franck-Condon principle. the motion becomes anharmonic and the energy levels are not equidistant as predicted for simple harmonic motion (equation 4. This situation is true for higher vibrational levels but (4. But in condensed Internuclear dtstance system and for large molecules rotational structure is blurred and the Figure 4. I+. I is the n-oment of incrtia. *Henceforward potential eneray will be abbreviated as PE. etc. is given as D. of the system is the sum E= Ec + Ev + EJ 160-600 20-40 r* 0. hence its equilibrium geometry. 1 c 0.1). Intensity The total energy E. If the vibrations are assumed to be simple weakened and at a certain value.3 POTENTIAL ENERGY DIAGRAM of v are represented diagramatically in Figure 4. of the bond strength The potential energy P t * curves for I. 2.02) kcal kcal kcal On electronic excitation. Using the spectroscopic convention of writing the higher energy state first and double prime for the ground state.4) for the zero vibrational level. a is a constant and (r . represented by Morse equation. the net vibrational motion of N-atomic molecule can b: resolved component atoms. the restoring force is motion is more complex. the depth of the minima being an indication obvious that ia real molecules the vibrational oscillations are not harmonic except near the lowest vibrational levels ( v = 0). molecule for the ground and some excited energy states are given in Figure 4. the relative contributions of kinetic and potential energies change as the about which approximately harmonic vibrational oscillations occur. vibrational should be because with increasing vibrational energy. Analysis of the rotational fine structure in absorption and emission spectra can help to establish the symmetry of the molecule in the given excited state. the situation is reversed. 1 t 1 etc. Therefore.re) is the extent of displacement from the equilibrium internuclear distance r. 2 c 0. This is as it The representation as a two-dimensional pote1:tial energy diagram is b p l e for diatomic molecules. Rotational fine structure can be observed for rather simple molecules in the gas-phase at low tem- peratures only. nature of the excited state can be inferred from the analysis of the \?..08 kJ/mo!e kJ/mole kJ/mole (40-1 40) (5-10) (~1!0. The most probable separation between the atoms is the equilibrium where D. The vibrational energy levels are usually represented as horizontal lines across the potential energy curves. the molecule dissociates into its harmonic. .

the reciprocal of the radiation frequency. This most probable transition appears as the most intense absorption Figure 4. the most probable transition during the act of light absorption is that. btween vibrational levels are about 20 kJ mol-l and thermal energy under ifaboratory condition is approximately 4 kJ mol-l. Therefore. It is evident that the population is energy surfaces. On the other hand. molecule in ground and higher energy line at a frequency given by Bohr relationship AE=hv.b. The wave function for the zero vibrational level has a maximum in the centre. Since they are less probable. This principle essentially implies that it is difficult to convert electronic energy rapidly into vibra- tional kinetic energy and the most probable transitions between different electronic and vibrational levels are those for which the momentum and the position of the nuclei do not change very much. these absorp- ." kb not expected to be populated at the room temperature. The time taken ' for an electronic transition is of the order of s. In photochemical studies where large number of excited controlled by the ratio AEIRT where RT is the thermal energy. 4. obtained from the Maxwell-Boltzmann distribution law: tion of the 3N-6 normal coordinate system.. For elec- states are involved in a single act.*zero vibrational level is mostly populated with only few molecules occupy- LL*ing the higher vibrational states. If a transition 8-lid state mtenti. and use the simple representation for the potential !A* difference between the two.2). the nuclei have nearly the same relative position and momentum as they did just before the transition. only the vibrational and rotational motions increase to the extent that the molecule may dissociate (pyrolysis) .4 SHAPES OF ABSORPTION BAND AND THE FRANCK. again the . e excited to the higher electronic state. the transition process can be represented by a tertical line which is parallel to the potential energy axis and originates from the lower potential curve to the upper curve.qmountof thermal energy is supplied. . the time period for vibration is about 10-lSs which is nearly 100 times as slow. which originates from the centre of v=O vibrational level.+ere No. 94 FUNDAMENTALS OF PHOTOCHEMISTRY @ys~cAL PROPERTIES OF THE ELECTRONICALLY EXCITED MOLECULES 95 linear molecules). N are the populations of lower and upper states and AE is the modes as 'frozen'. As a consequence. tion lines are of lower intensities. ~ f o rbeing I . those molecules which CONDON PRINCIPLE are able to reside in higher vibrztional levels as a consequence of the Boltzmann distribution add to the vibrational transitions of lower proba- At tempratures most o f the molecules reside in the zero vibra- tioml'eve'of bilities giving the familar contour of an absorption band. Few transitions states. The energy difference .3 Potential energy curves for I. the internuclear distances do not change during the act of light absorption.1 funetj0. To represent the variation of potential energy as a func. representation by potential energy sur. Hence. I. tmnjc levels A E is 160-600 kJ mol-' and the electronically excited state faces is avoided. we need 3N-5 dimensional hypersurfaces (one extra dimension for representing the potential energy). . the best that P can be done is to consider one or two modes at a time. Therefore. This fact forms the basis of formulation of the Franck-Condon principle which is stated as follows : Electronic transitions are so fast (10-l5S ) in comparison to the nuclear motion (10-l3 s) that immediately after the transition. But such a surface is beyond our visualization. Thcre- fore. considering other . Furthermore. indicating the region of maximum probability (Figure 4. If a large . T~~ infomation is occurs to a positron corresponding to energy greater than the excited state . . are also possible frbm the other positions of the v=O level adding to the width of the absorption band.

AMENTALS OF PHOTOCHEMISTRY PROPERTIES OF THE ELECTRONICALLY EXCITED MOLECULES 97 dissociation energy.96 FUND.4. The width of the progression is determined mainly by the range of values covered in v = 0 level which in ultimate analysis is governed by the rtainty principle (AE x A t z 1). This is known as pred/ssociation. Hence. If a different equilibrium bond length is indicated in the excited Wegral is known as the Franck-Condon integral and demands a consider- state PE function.5 illustrates good and poor overlap of wave fhnctions. For the internuclear geometry as represented by the potential energy nuclear and electronic coordinates are separable (Born-Oppenheimer (PE) surfaces of the ground and excited electronic states in Figure 4. the above factorization is justified. imum for v = 0 wave function of the ground state. the shape of the absorption contour as defined by the vibrational masition to that energy state will be most probable for which the terminal intensities. On coordinates also (rotational coordinates are neglected). an excited and a ground state molecule may be formed. The Franck-Condon overlap cri!erion . the &proximation) and the electric dipole transition involves the electron' vibrational excitation to 17'=2 level is coupled with the electronic transition. overlies vertically above the function with respect to the ground statc function (Figure 4. 4.5 Good and poor overlap of wavefunctions of two potential energy surfaces. wrdinates only. the continuum may be in the far UV region.'xr dr.3). the transition moment integral must include Iysis) and discrete vibrational bands are not observed (Fig. is governed by the shape and disposition of the potential energy imum of the upper energy wave function. I n some molecules a blurring of the spectrum appears 4. The intensity of giving an intensity distribution pattern as shown at the upper left side of @sition is observed to deprnd on the integral j x. The Thus. 4 ~ ) . the molecule dissociates directly on excitation (photo.Geed overlap --L* overlap I I m-n I I n-o Figure 4. the shape of the absorption curve will change accordingly.2 Crossing of Potential Energy Surfaces Figure 4. An understanding of the For transitions in which electronic transitions are coupled with . it is of photo- *mica1 interest. For polyatomic molecules of photo- chemical interest.4. photodissociation.p*:mPortant for an understanding of radiationless or nonradiative &ansitions as well. a continuum is more likely to appear for simple diatomic molecules.2.4 Internuclear configurations and shapes of absorption bands. ---.4 b. This the figure. the excess energy being converted into the kinetic energy of the partners. tional transitions as well.1 Quantum-Mechanical Formulation of the Franck-Condon Principle t before the dissociative continuum suggesting dissociation at a lower energy Rquirement.4). Since kinetic energy is not quantized. &e overlap of the wave functions of the two combining states. as we will see in Section 5. The beginning of the continuum in the absorption spectrum of simple c &as-phase molecules iqplies the dissociation of the bond in question (Figure 4. also. 4 . Figure 4.

Because of the nature of If the potential energy surfaces of an electronic state into which a wave function in v' = 0 state and the Boltzmann distribution of energy in molecule is excited on light absorption ia crossed by that of another at the excited state. excited state. On the return transition. for about s for an allowed transition and more for a partially forbidden transition. Once the molecule is transferred to the second . In general. 4. and E.7). Such transfers have time periods a~trum with a region of overlap.?ymmetry operations can and may increase the chemical reactivity and subsequent course cross.. 0 -t 2. For polyatomic molecules and molecules in the condensed state. energy state is formed as a compressed molecule according to the Franck-Condon we written as 0 + 0 . there is a distributio~~ of frequencies around the 11i0st some point higher than v' = 0. goes over to that of S. If a simple molecule dissociates into fragments from in predicting the physical and chemical behaviour of vibronically excited excited state at least one of the partners is likely to be molecules. it may dissoc'ate or behave as dictated by the PE surface of sequenc.. the molecule may transfer into the second I probable transition. These ideas can only be applied qualitatively to polyatomic molecules "because of the lack of structure in their spectra. equilibrium internuclear equilibrium geometries of the molecules in the two states. (Figure 4. etc. When the absorbed energy exceeds that of the when the potential energy curves of a molecule are drawn.. In the case of atoms or simple molecules at very low pressures 'where collisional perturbations are absent.2. If it is permitted to return to the ground state by Figure 4. the excited species may return $0 the ground state directly by emitting the s a n e frequency of radiation rs it has absorbed. associated with reverse transition of electron ground state molecule.es of crossing of potential energy surfaces which play a big role 'tbs second state. A frequency v. -- lis quickly lost to the surrounding in a time period 10-l3 s. The mercury msonance radiation at 253. Q ~ S I C A LPROPERTIES OF THE ELECTRONICALLY EXCITED MOLECULES 99 origin of predissociation spectra can help us to appreciate the con.6 Noncrossing rule of Teller for potential energy suxfaces.. I ~tbe fluorescence there is a possibility that the molecule.state to the other at th: point of intersection is governed by the selection rule for radiationless transition which will be discussed in Section 5. will lie in the plane of = greater than vibrational time periods 10-la s but less than the rotational Ule mirror image symmetry defined as time period3 = 10-l1 r. it again follows the Franck-Condon principle and arrives a t a higher vibrational level of the ground state. The mole- cule comes to stay at the zero vibrational level of the first excited state . At the crossing point (isoenergetic point). radiative transition Juorescencc emissio~z is observed. The transfer of the molecule from one excited crossing. The molecule initially excited to S.. 0 -t I. the excess energy appears as the kinetic energy of the completely identical characters with respect to ail . if there is good overlap of ground state A E ..e. Figure 4 . as in many polyatomic molecules.5 EMISSION SPECTRA The emission of radiation is also governed by the Franck-Condon 'p&cipl:. I I If the internuclear geometries are not very diffe- vibrational wave functions. no two levels with dissociation limit. F . The most probable transition again depends on the elactronic state by a nonradiative mechanism. internuclear distance r. Franck-Condon overlap integral is large. the mcess vibrational energy gained in a vibration-coupled electronic transition.. the &sorption spectrum correspond to vibm~ional energy diffelences AE. instead of moving along the PE ' t ~ t r u mappears as a rrzirror it.. Since a few vibrational quantum states are also excited. . .7 nm in due to such transitions. It is akar that whereas the spacings b-tween the vibrational band in t l x principle. i. 0 -+ 3. This is known as resofiance radiation.mission. We might d o well here to define the noncrossing rule of Teller: electronically excited. molecule immediately starts vibrating along the potential well of the state h the excited state.zagc of the corresponding absorptiol~ surface of S. 6 illustrates the PE surfaces which cross and which avoid of the chemical change. *nt. those in the emission reflect the energy differences in S.. since what is probable for absorption must be probable for . . for the excited state is greater than that for the The vibrational transitions.

It is important to realize that the origin or 0 . +. In large molecules. In gases. liquids and Ions the perturbation must be averaged over the molecular he van der Waals interactions include (i) London dispersion force actions. If the system mction A has the opposite effect. the former. v . The dispersion force a Wavelength . excited state. (v. Dispersion force interactions are present [Adapted from Ref. A shift in the spectrum may result due t o such rences in the two combining states. such as carbon-halogen bond polarizability in halogen-substituted pounds. In the Nkd orbitals of the neighbour. The attractive interaction B tends to stabilize the than the size of absorbed quantum. The resultant shift in energy AE is crosses over t o the triplet state subsequent to promotion to a singlet sum of these two opposing effects. In solution. . These are attractive interactions. r the distance between the interact- independent of the ex-itiog wavelength & moleculen with their respective exponents and the summation is over %h neighbours. uids.So absorption band. whereas the repulsive longer wavelength. eraction with the environment affects differently the various electronic of a molecule. here are two types of solute-solvent interactions: (1) universal raction. In general. Since the size of the emitted quantum hvj is smallef he orbital size. 2F .explaining the spectral shift.v f ) z 0 and the extent of s h e interactions have larger coefficients in the excited state. The universal interaction is due to the collective influence of the solvent ~bsorptl'm F tuoresence phosphorescence dielectric medium and depends on the dielectric constant D and the active index n of the solvent. This is known as the Stokes shifr. is more important than the overall molecular polarizability Figure 4 . X] p e n for nonpolar solutes in nonpolar solvents. Reasonably large environmental pertur- s may be caused by van der Waals dipolar or ionic fields in solution. fluorescence and phosphorescence spectra. and vj are frequencies or"absorption and emission. = vj = v. in solids or in gases at high pressures. The repulsive interactions are primarily derived from exchange forces bonbonded repulsion) as the electrons of one molecule approach the v. (ii) induced dipole interactions.0 band is expected to be affected differently from maxima if they do not nearly coincide. The spectrum shifts towards low frequency region . PUNDAMENTALS OF PHOTOCHEMISTRY ICAL PROPERTIES OF THE ELECTRONICALLY EXCITED MOLECULES 101 ':%6 ENVIRONMENTAL EFFECT ON ABSORPTION AND EMISSION SPECTRA Because of the variation of electron density in different electronic states. because of the increase the ground state. and (2) specific interaction... emission occun from the thermally equilibrated upper state. both the attractive and vapour phase. overlap varies depending on the PE surface of the upper state relative to use of the greater polarizability and the latter. actions depend on the molecular polarizability which increases with lectron density in the molecule. 7 Origin of absorption. (hvj < hvn) emission occurs at a ted energy state with respect to the ground state. the local pola- ility.1 . image rclationrhip with S. and (iii) dipole-dipole actions. hv. respectively. emission may be observed at a still longer wavelength. .111s is known as phosphorescence emission and does not show a mirror . the *re AA and AB arc differences between the repulsive and attractive intensity distribution in fluorescence and phosphorescence spectra is M c i e n t s in the two electronic states. Since in condensed systems.

In the excited state. fluorescence and absorption spectra are influenced by interaction with the (0 (1) . it is expected to differ in $4.8 Solvent red shift and blue shift' in absorption spectra. The London forces are alwaqs . therefore. rr k H y ~ ~ C A KPROPERTIES . The short range interations such as H-bonding is neglected.the use of solvent perturbation technique for the identification In the ground state. If there are low lying unfilled #ates. OF THE ELECTRONICALLY EXCITED MOLECULES 103 when AE is negative (red shift). in solution it is depressed by an amount proportional to R. produced on such than that of the ground state and the excited state is. The line spectrum at low temperature in the vapour . present. and a is the radius of the cavity in which the solute solute in the ground and excited states are also expected to be different. te (FC)*.+ ' If the solute molecule has a dipole moment.8. In polar solvents. is hydrogen boncteci In the ground state. it is likely to have a strong affinity for electrons. NOW. the dipole moment may not only have a . These involve short range forces. A charge- transfer (CT) state has a much greater permanent dipole moment than the ground state and. hl) #e'8'g.8). f:&roadening also results due to thermal vibrations. and the refractive index n of the solvent and the difference (2) Many solute-solvent interactions are somewhat more complex and lb dipole moments of the solute molecule in the two combining energy speczjic than the one discussed so far.0 transition due to solvent interaction in the two of solute-solvent interaction is the formation of hydrrog~nbonded colplplcxes q%tates of different polarity can be explained with the help of Franck- and ~xciplexes. The latter is defined by Onsager9s reaction field If it is greater in the ground state then the ground state energy level is stabilized and blue shift occurs and vice versa. the vibrational structures of the . .:getely lost in solvents which can specifically interact with it.. If the solvent is nonpolar. ipto the x*-orbital reduces the hydrogen bonding forces in the excited state. This results in greater decrease On excitation. x*) excited state is more extended constant D polarizes the medium. The donor capacity of the cules respectiveIy. The shift in 0 . the energy shift be- extended molecules. a charge-transfer- to-solvent (CTTS) complex is said to be formed. The reaction field R.7 EXCITED STATE DIPOLE MOMEKT various electronic energy states because of the differences in charge distri- ' The effect of solvent on the absorption and emission spectra may give bution. change to a polar solvent results in a considerably larger red shift. therefore. The result is a blue shift as illustrated in Figure 4.*solventenvironment. h l <ha2 d$phaseis usually b r o a d e ~ e dand sometimes its vibrational pattern is com- (red shtft) (blue shllt) . and p. of ( n +x*) and (x -+K*) transitions can be rationalized. eondon principle (Figure 4. the molecule is promoted to the Franck-Condon excited in ground state energy for more polar and hydrogen bonding solvents.*rg h. the filesiding in a spherical cavity of radius a in a medium of static dielectric electron charge distribution of a (x. On the $IfSo is the unperturbed vapour phase energy level of the molecule in the other hand. in n-+ x * transition. then the rough description of the interaction is dipole-induced dipole type. kolecule resides. In addition to the spectral shifts. point '~@&eories have been worked out in terms of Onsager theory of dielectrics dipole approximations are made which are poor description for large :&d Franck-Condon principle. dipole-dipole Cr :useful information regarding such physical properties as dipole moment interactions also become important. The charge-transfer complexes bridge the gap b e t ~ e e n weak van der W a ~ l scomplexes and %here p. Some : Figure 4. more 'Fteraction is polarizable. ri orbitals in the solvent. Change to a polar from a nonpolar solvent increases the solvent interaction with both states but the corresponding decrease energy is greater for the excited states resulting in the red shift. For the calculation of dipole-dipole interaction energy. Still another specific type- "qssuming the solvent as continuous dielectric. nonbonding lone rair on the heteroatoln [*ound state.9) for absorption and emission processes.jehanges and polarizability of the n~ol:cule in the two combining states. h e n the 0-0 band in absorption and emission is related to the dielec- b#gicconstant D. In general. and towards high frequency region when The excited state is not much depressed as the promotion of the n-electron A E is positive (blue shift) (Figure 4. If the solvent accepts electrons from the solute molecules. are dipole moments of the ground and the excited mole- molecules bonded by strong valence forces. According to t$ese. a solute molecule having a dipole moment p.

the FC ground state relaxes to the equilibrium ground state. The Onsager's field is - (v~hs-''~ ).E) (4. .11) and (4. the ground state solvent orientation will not have the time to change in tune with the For a nonpolar solvent D z rz2 and the interaction energy is zero.15) ~d (4. polarizes the solvent and the solvent molecul~sadjust to the new situation. o Acetone o GlVcol therefore.0 fluorescence a gergies is obtained from the two relationships.gy in the gas phase. If the average lifetime ~f of excited state is grsater than the dielectric relaxation time TD then excited state dipole moment p.. ) ~ / ha3c from which (p.~ . pg) + (4. 1s obtained as E q a ~ l ~ b r ~ground um state Figure 4 .12). (4.). The FC excited state (FC)* is stabilized by this amount to give equilibrium excited stat.16) the final expression for A i.14) bf"h-r. = h e (Go-V/) - = (Ric Ro .1 Figure 4.e ~ g ) (4.)~is the ene. D-1 rz2-1 different magnitude. The reaction field in (FC)* state is dope is given by 2 . 9 Effect of refractive index and dielectric constant of solvent on 0-0 transitions of a polar molecule. The energy of absorption is.RFC R*) (p. but different direction albo.JOs (h vf). Only the electronic polarizability is affected immediately < When the quantity A is plotted as function of A f of the solvent the on excitation. 4.. h c ~ .p.--' F ranck-Condon exclted state ginally. r m . p. A reaction - 0 chloroform field is produced.13).the difference in the 0-0 energy absorption and emission.: S. the difference in moments for the two states involved in the transition. FUNDAMENTALS OF PHOTOCHEMISTRY i' $jtfiYSICALPROPERTIES OF THE ELECTRONICALLY EXCITED MOLECULES 105 T-c3 $he energy of the 0-0 transition in emission is given as + h vf = ( h vf)o (RFC. given as va = ( A va)o + (R& .. and expressing in wavenumbers. The 0-0 fluorescence transition Carbon occurs from this energy state. Since the electrollic where 2D+ 1 21zz+ I transition is much faster than the dielectric relaxation time. Again a strained ground state (FC) is Hexane tetrrrchlor~d~ produced in accordance with the Franck-Condon principle in which solvent 20 30 40x10~ orientation does not have time to change.14) assuming (hY. (4.11) where ( h v. new situation. where n is the refractive index and n2 is equal to high frequency dielectric constant at the frequency of absorption.p.10 Plot of (G-G) vs Af=[2(D-1)/(2D+l)-2(n2-1)/(2n2+1)] . The difference between 0-0 absorption and 0.15) - a substituting the values for the reaction fields from (4.R*) (pe .Ro) ( ~ . can be calculated a f 0 E *ac.

the 0-0 separation can also be affected by environmental modification of the potential energy surfaces.rf of the molecule.5 23. If the bn R-* is capable of emitting fluorescence.6 32 baracteristic of the ionized species was observed at a pH where the p-dimethy lamino-pl-cyanostiIbene 8 23 6.and mela-positions. it suggests that the . Many such examples will be presented in appropriate places. it is a very useful ~a benzene ring. a difference results agree with more rigorous calculations (Table 4. On h d the constant is designated as pK*. Absorp- distribution explains the weak acid character of phenol and ortho-.3 in the ground and excited states.106 FUNDAMENTALS OF PHOTOCHEMISTRY F S I C A L PROPERTIES OF THE ELECTRONICALLY EXCITED MOLECULES 107 I. tion and emission characteristics of RH and R.ted The acidity constants in the excited states provide rather direct molecule. If pK* <pK. the charge density on oxygen is teduced and a reasonable charge made..). Therefore. (Czekeila) and the equilibrium constant is expressed as pKa value (. which @ ~ s i t yis now found on ortho. Besides the relaxation effects. 8 EXCITED STATE ACIDITY CONSTANTS-pK* VALUES the ion is observed but the absorption is characteristic of the undissoc.10). and para-positions of the benzene ring. 4 . be obtained from MO calculations.2 'fiiod less than the lifetime of the excited state. hv.1).lO-trisulphonate. RM* +H20 + R-* PISO* tures. A lpknol is more acidic and is also oriho-meta-directing towards substitution negative sioi~leis obtained in the reverse case. a positive slope is obtained (Figure 4. t 1 PK* hvr Such s o l v e ~ perturbations ~t are largely responsible for the variation of photochemical behaviour of a molecule in different solvents. In the first excited singlet Utilize this method for the evaluation of pK and pK*. TABLE 4. within certain pH range fluorescence due to RH* measures of electron density distributions in the respective energy states. This is a proof of proton transfer in a time p-amino-p'-nitrophenylt 6 0 22. A maximum value for A< ( 0 . . and R-* bath are observed (Figure 4. This may decrexe the 0-0 separation between absorption and emission.rd may be larger than the mean radiative lifetime .. This the ground state pK can be calculated from absorption studies.11).in the p-amino-p'-cyanodiphenylt 6.4 !gbund state is represented as: p-amino-p'-nittostilbenet 6.O -+ PhO. the other hand. the representation is At high viscosities or low temperatures. excited is normally the case. at high temperatures solvent relaxation may be promoted equilibrium is shifted towards the right on excitation: thern~ally decreasing ~d and 0-0 separation may again decrease. The equilibrium between an acid R H and its conjugate base R. A molecule which is undissociated in the ground state at a given pH is dissociated on p r o m ~ t i o nto the higher energy state. on 0-atom and ortho-.H. para. The pH value at which the The charge distributions for phenol in the ground and axcited state can two intensities are nearly equal give the approximate value for pK*.O+ + The phenomenon was first observed in 1-naphthylamine-4-sulphonate Dipole moment of some compounds in the ground and the excited states by Weller who found that the fluorescence of the compound changed golour with pH. respectively. 3 pK units. Fluorescence p-dimethylamino-p'-nitrostilbene 8 24 7.characteristic fluorescence of 4 .1 + PhOH H. if a reasonable assumption about the radius of the Onsager's cavity a be btste. Thus.log K.0 and 5. cnited state dipole is greater than the ground state. High electron densities are observed since absorption wavelengths for the acid and its ion are also different.1 29 #&teroatom is not dissociated in the ground state as indicated by its Dimethylaminonaphtheurhodin 7 10 2 12 #ktracteristic absorption.must be different to directing property of the hydroxyl group. If the. dielectric relaxation time . 8. because the order of energy levels may change with change of solvent. Therefore.0 13 0 tMeasured by fluorescence depolarization studies. although the absorption spectrum was not affected.An explanation of this observation was provided by Forster for a '8milar observation in 3-hydroxypyrene-5. Compound a (in A) AP Debye t*g Debye PC Debye .0 ) is expected at some intermediate tempera. The protolytic equilibrium constant pKa for the reaction method for the determination of excited state dipole moments and the % 10. In the excited state.

12). aldehydes. (c) pH 7.0 absorption energies of the acid RB and its ion wicyclic acids.12 we find. But in the excited states respectively.. the change of From Figure 4. respectively. internal proton transfer occurs when carboxyl and the acid and its conjugate base.=AH-AH* (4.12 Forster's cycles for pK and pK*. HA-undissociated acid. Hence. The effect is not observed in ortho or para data agree within experimental limits. nitrogen and sulphur heterocyclics become stronger bases. and AH* are enthalpies of proton dissociation in the ground and the Asconjugated base. (b) pH 9. A S z A S* then. carboxyl p K .me A .p K . we have the excited state. the shift is small. pH values within which the fluorescence colour changes are observed. 'corresponding ether.3 expressed as Hammett's acidity function H. 0.23) In general. On rearrangement. hpK*=pK-pK*= ~m (4. RJNDAMENTALS OF PHOTOCHEMISTRY ' ~ Y s I C A LPROPERTIES OF THE ELECTRONICALLY EXCITED MOLECULES 109 Figure 4. of the orde. This compound exhibits large Stokes' shift. is El+AH*=E2+AH (4. are 0 .1 N NaOH. thiols and aromatic arnines become much stronger acids on excitation. +homers of salicyclic acid.AH* acid is more basic or less acidic in the excited state. .h c ~ . aromatic carboxylic acids exhibit a decrease in AH=AG+TAS (4. phenols.respectively. w. For AH*=AG*+TAS* (4. 1 excited states. Intramolecular proton transfer has been observed in molecules like where El and E. But if the proton dissociation is a slow process. If AH Figure 4. AH-AH*=AG-AG* = - R T (In K . pK* can be (z. 3 RT 2.21) example.In K*) (4. protonation occurs at pH zero suggesting that benzoic A H . ketones with lowest Depending on the ground state and excited state enthalpies. then In contrast to alcohols.25) lifetime ~ fthe . (4.20) acidity in the first excited singlet state relative to the ground state. But in the R. 1 N HCI.26) ~licyclicacid is rationalized if we assume that upon excitation. A more general method proposed by Forster is a thermodynamic calculation based on a cycle called after his name (Figure 4. The unusually large shift in *-E1-E2 .24) rmall.of Or. greater than.2 .x*) singlet. pH range may be considerable.22) where K and K* are protolytic equilibrium constants in the ground and ~ n l yat pH of -7. equal to or less than pK. If the protolytic equilibrium is established at a very fast rate.is the difference in electronic transition frequencies (in cm-l) of As a consequence. benzoic acid can take up a proton If it is assumed.3 RT Woup becomes more basic and the hydroxylic group becomes more acidic. El-E.11 Fluorescence spectra of &naptho1as a function pH: (a) pH 13. (d) pH 0. In ether such hydrogen to hold true because pK* calculated from emission data and absorption h d i n g is not possible. while carboxylic acids. The assumption AS z AS* is considered bdroxyl groups are hydrogen bonded internally.

5 2-Naphthol 9.2 10-12 4. then taking the average value.9) are more basic in triplet state than in ground state. light The pK* values of phenols in singlet and triplet states are valuable Me + 2Fe+f + 2H+ .T PK.62 of some organic molecules A A . the acceptor has a much excited state acidities frequently follow the Hammett equation fairly well if lower electron affinity in the ground state than the donor.0 4. The (FeJ+/Fe2f). E. - f r ~ mdifferences in solvation energies of the ground and excited states. In such electron transfer reactions. calculated values from absorption and emission data are: TABLE 4. specially for the aromatic The electrontransfer in the excited state is reversed when the molecule hydrocarbons. oxidation potential of the dye increases and the ferrous iron is 2-Naphthylammonium ion 4. Kuder and W.1 . tion in the triplet state..6 But when excited in the presence of Fe2+. the dyes cannot oxidize Fe2+to Fe3+. Fluorescence max.72 (from fluorescence data) (average value) This difference in ApK* values as obtained from absorption and emission data arise PK. In general. Wychich-Chem.8 4. 1-Naphthoic acid 3.1 oxidized t o ferric state.0 .'s.2 first triplet states are observed in the oxidizing powers of methylene blue and thionine. the excited s t a t e p ~ z= 1.03 (from absorption data) Singlet. have been obtained by Porter and his Average school from phosphorescence studies.1 -2 3. Lett24 (1974) 69)' For merocyanine dye 4'-hydroxy-1 -methyl stilbazolium betain. . A similar system includes mixed inorganic solutions such as (I.. It follows that the singlet transition in these molecules has considerably more charge transfer character than the transi. x 10-a cm-1 vb x 10-3 cm-1 in the first excited singlet state. The colour returns on removal of the excitation source. Phys. the dye itself being reduced to the leuco form.5 3. p~z. following resonance structures are possible: The triplet state acidities. triplet and ground state acidity constants of some organic molecules are given in Table 4. i f the 8./I-) + without change in the direction of conjugative substituent effect. leucodye + 2Fe+++ guide t o substituent effect in the excited states. Triplet state acidities. J?K.~ (flash spectroscopy) (phosphores- cence) ground state pK.85. the colour of the dye is bleached. dark MeH.1 8. 4. 8. Absorption max.1 7. In the ground state.3 3.5 10.T PK. At T = 298 K .6 5.9 EXCITED STATE REDOX POTENTIAL Phenol 10. .2. -. The From Forster's cycle singlet. triplet and ground state acidity constants p ~ =z 4. the conjugation between substituents and -returns t o the ground state. In the long lived Quinolinum ion 5. the leuco dye being oxidized back by ferric x-electron clouds is very significantly enhanced by electronic excitation ion.0 4. Acridinium ion 5. using flash photolysis techniques.6 .2 A~K: 9. are found to be not much different from The wavenumbers of absorption and fluorescence maxima at two differen acidities are: ground state pK. 6. But I-eterocyclics like o-phenanthroline and quinvline 1H+ (in acid) I (pH 9.8 triplet state. Thus.57. PK. 6.7 10-12 3. the 'exalted' substituent ccqstants o* are used.7 Examples of striking differences in redox potentials between ground and 2-Naphthoic acid 4. FUNDAMENTALS OF PHOTOCHEMISTRY WYSICAL PROPERTIES OF THE ELECTRONIC4LLY EXCITED MOLECULES 111 gxample (J. although less basic than V.0 5.

A limiting value is obtained in rigid glassy ~lvents.29 j photoredox reactions which are reversed in the dark. are available in living systems.70 + 0. singlet and triplet. codigurations of dye in its excited states. triplet and singlet state (a) (b) (4 energies of the dyes expressed in kJ mol-'. Z ' The oxidation potentials of the short-lived dye intermediates may be estimated with reference to polarographic half-wave potentials.18 .rM-) reduced forrn. & Kepka.42. Photochem..13 Electron configuration of dyes in ground excited singlet and tripkt states and in oxidized and reduced forms: (M)ground singkt.1. E 1 ( S + / S ) E' (*IT) to higher level by absorption of sunlight by green chlorophyll molecules Dye kJmol-1 klrnol-1 volt volt volt volt of the leaves are made to synthesize complex plant products from simple bfiflavin 214. ~.1. The process is endergonic and is only ? p i d i n e Orange 206. In crystalline solids with fixed molecular orientations.67 + 0.) are polarographic Dcpolar~zed Partially polarized r lane polar~zed half wave potentials.47 -1. Photochemical redox reactions are r Es the basic photosynthetic mechanism in plants.1. ~ S I C A LPROPERTIES OF THE ELECTRONICALLY EXCITED MOLECULES 113 112 FUNDAMENTALS OF PHOTOCHEMISTRY TABLE 4 . Many such examples of dye sensitized 197.35 . #bdegree of polarization of emitted radiation is much reduced.1 247.1. CM+) oxidized form and (IM)excited singlet state.61 -0. In case bf solutions of such molecules. L .37 possible on photoexcitation.27 molecules like CO. partially polarized and completely polarized radiation.0 201.0.14 E l ~ t r i cvector representation of completely depolarized. .('M) triplet state.36 + . are anisotropic and randomly distributed in space.77 + 0.6 163. respectively. ?pssweiner.67 . .62 -1. ionine 190. an oscillator which vibrates with the same the emitted radiation is also plane polarized. standard hydrogen electrodehas a value -0. The electronic lier. the direction of transition moment. 10 EMISSION OF POLARIZED LUMINESCENCE The computed values of oxidation potentials for some dyes are given in From the mechanism of absorption process (Section 3. G . and in oxidized and reduced forms are given in Figure 4.1 0.14 a). and H.1.e. A beam of radiation is said to be depolarized if the electric vectors are a h n t e d in all directions in space (Figure 4.O. I . i. The potentials E' (volts) correspond to pH 7 reference to which photon of proper frequency only if the polarized with its electric vector parallel to the Relerence energy j axis.6 +0. it is evident Table 4.53 light energy. ET and ES are. whereby electrons promoted ET E' ( S / S .08 -1.96 + 0.79 -2. the fluorescence has been found to be hmpletely depolarized in solvents of low viscosity but partially polarized b more viscous solvents.1. A .e.2 234.1). For an isotropic orber or oscillator. 305. perpendicular to the Figure 4. the degree af~olarizationdepends on the angle of orientation of the molecules in the WYstal lattice.61 .3.4 + 0. They provide a mechanism for photochemical storage of .36 . 3 oxidation-reduction reactions on excitation goes against the gradient of Oxidation Potentials E' at pH 7 of some typical dyes electrochemical potential AG > 0. Figure 4.13. Photobiol. i. E 1 ( S / S . .7 230. if it -is Electron-transfer was suggested by Weirs as a mode of quenching of assumed that the free energy changes are mainly due to the occupation of and it appears to b: a more general mechanism than considered the highest filled and lowest unfilled molecular orbitals.70 .) E (TIS. 16 (1972).3 +0.4 220.

the emitted radiation electric vectors of a plane polarized radiation vibrate along OZ in the ZX ha\ e been completely polarized.14 c). (a) in emission will be parallel to the electric vector of vibrate with electric vector in one plane (Figure 4. The electric &ends on the properties of the molecule and the directicn of obarvrtion. The extent of this effect can be When a solution of anisotropic molecules is exposed to this plane timated by decomposing the emission electric vector into parallel (I. The molecule'(a) will absorb with maximum probability A and intensity of absorption is A'.16) (App. n l l e land perpendicular to the incident electric vector direction respec- Under favourable conditions these excited molecules eventually return gvely. The degree of depolarization is given as the ratio and can be nicely illustrated for anthracene molecule(Figure 4. If the emission is in random orientation.15). which is considered perpendicular to the plane of the paper. The greater the of emitted radiation mgle 6. ' e e r v e d along O Y direction. In a partially polarized beam. Polarization direction OZ. as it is measured an observer. 2 4 r 3-P '' (4.z p~= . and the intensity of absorption by cos20.4) curve for intensity of fluorescence emission from randomly oriented molecules excited by polarized radiation. the molecule (b) will have lowered probabi- p = 4 1- + -11 41 I 1 ' r = r ~ ~ . (perpendi- Figure 4. the electric vector will find the solute molecules d perpendicular (IL)components (Figure 4. The degree of polarization p and anisotropy r is defined as nm radiation creates a transition dipole along the short axis of the anthraceoe molecule.) polarized radiation. If the excited molecules do not rotate within their k t controls the probability of absorption and hence the intensity of lifetimes.1 5). The 365 11I 1 1 .=90". The e.I 21.- + I.. 1).16 Polar (r. the larger is the perpendicuIar component in the emitted radiation Pusing d.15 Probability of absorption and emission by differently oriented anthracene molecules. the majority of waves will !& . The integrated . emission oscillator will be maintained. But the oriented molecules plane and OX is the direction of propagation of the plane polarized wave.27) lity of absorption. are the intensities of the components of the beam.3r and r . Those molecules which are oriented by an angle 0 to this direction will have their absorption probability reduced by a factor cos 0. IF all the molecules were aligned as in (a). Finally. the electric vector of The polarizltion of the total fluorescence radiation.14 b) and in a completely fDcident radiation. f).:polarization. the molecules oriented perpendicular to the electric vector will not absorb at all. ace uniformly all around with the molecule as the centre of dis- Let the coordinate system be such as that given in Figure 4. These statements are direct consequences of directional nature of light absorption Figure 4. The emission defined coordinate system (Figure 4. ' ~ . that of molecule ( 6 ) wiIl maintain an angle and the polarized beam all the vibrations are unidirectional with respect to a lecule (c) will not emit as it did not absorb (Figure 4. The polarization of fluorescence emitted by an individual molecule to the ground state by emission of fluorescence radiation. the angular relationship between absorption oscillator and horescence.114 FUNDAMENTALS OF PHOTOCHEMlSTRy WL PROPERTEE OF THE ELECTRONICALLY EXCITED MOLECULES 115 direction of propagation. troduce some depolarizing effects. the molecule (c) will not absorb at all because 0 . propagation direction OX. A cos 0 and the corresponding intensity A2 cos" and *re Ill knd Z. Only those molecules absorb with maximum probability which have their transition moment oriented parallel to OZ (photoselection).cmolecul.15. vector of emitted radiation will be parallel to the transition momellt of oricrtta'ion with -cspect to the direction of polarization of primary emission oscillator. The dotted curves represent vector direction wr to the incident electric vector) will be introduced in the emitted irdiation causing reduction in the degree of polarization. results from superposition of all the elementary waves itted by all the randomly oriented excited molecules. a perpendicular component 11. Therefore.

the maximum degree of polarization p. the egree of polarization of fluorescence as a function of wavelength or wave- . whereas the lifetime of the excited molecule is of the order of ' lo4 s.113.33. the second curve is that for parallel component (Ilr)and the outer r solved in a rigid glassy medium of infinite viscosity.29) corresponds to the intensity distribution for the perpendicular component (Il).17A). Obviously. this condition will no longer ption and S.. transition moments in different absorption bands of a given molecule from degree of polarization depends on the average period of rotation polarization of the fluorescence e ~ ~ i t a t i ospectra. These reflect the relative orientation of #@betransition moments in the respective bands. The translational component of thermal agitation will have no t on the degree of polarization of emitted radiation.e. the emitting state is the same as hx In all the above arguments. OR is the total intensity and polarization po will be -0.mmber of exciting light. when 0 is small. The two components can be analyzed owest excited state. As a result. Therefore. The values are 113+ h d ~ e r o lor sugar solutions. q$nd 4 are polarized almost perpendicular to 1 and the polarization of 2 b! at some intermediate angle. n . For long-lived provide a suitable method for assigning the polarization directions of es (T large). although randomly distributed. But if With vertically polarized exciting light. A plot of po. for example.16 where 0 and 4 are as defined. If the exciting light is unpolarized. p~ becomes negative and is equal to . I. The molscule is IL = sin20 cos24 In the figure the sample under study is placed at 0. In the region of overlap between the two bands by suitable devices such as Nicol prism and Glan-Thompson prism. t So in absor- fixed in position. it has been assumed that the molecules the absorbing state. the emitted radiation may not be completely and -1/7 for unpolarized radiation. Thus. Thus. with p = 90°. the transition moment for absorption 1 410. absorption probability is high and the transition moment of the molecule.p transition moment in a is aligned along the vertically polarised exciting fight (j3 = 0) and in b it is at right angles to it (p = 90'). gtvel over the absorption band. the degree of polarization will be small. the absorption and emission oscillators may have different transi- . po = 4 when j3 = 0. gives the fluorescence polurization spectrum. But the rotational tion moment directions. If a less viscous medium is used. The greater the viscosity q of the solvent. asition in bands 1 and 5 have the same polarization direction. For unpolarized exciting light ' of lV1 s-l. but emission is from a lower energy state. The change in polarization from positive to negative value will be polar curve is symmetrical with respect to the axis OZ and will give three . bands 3 works out to be 4 for vertically polarized light. the in a direction 0 to the direction of excitation. But if the moiecule is excited to a higher energy state. in such a medium. In the second band b.= cos20 (4. But when -tion is hindered by putting the molecule in a viscous medium like j3 . For all possible values of 0 and 4. when observed at right angles to the direction of excitation.116 FUNDAMENTALS OF PHOTOCHBMISTRY effect of all the molecules will result in a polar curve given in the Figure Suppose a molecule gives rise to two aosorptton bands a and b corres- 4. The po value is given by "'during emission from that at the instant of absorption. the fluorescence fh Completely depolarized and spherically distributed in space.and Sz(Figure 4. greater in emission is perpendicular to that in absorption. S. In &e band a. each excited molecule on the average can ?"We about 1000times before it fluoresces.5 and will remain at this curve gives the total intensity in any given direction of observation. c So in absorption and T. in an infinitely viscous dium. The fluorescence polarization spectrum can be used to identify dimensional distribution function on rotation through 180" along this axis.. The viscosity. the extent of rotation during the 'Metime of the excited molecule only will be effective.= 4 2 . and P“riding to transition in two different energy levels S.1 Rotational Depolarization of Fluorescence coincides with that for emission. These observations R6u be the degree of polarization for a giben lifetime T. In the system discussed above.-+So in emission. for vertically polarized light where p is the angle between absorption and " The frequency of rotation in a medium of low viscosity is of the order emission transition moments. po = 4. The fluorescence polarization spectrum of Rhodamin B and the in the absence of any other depolarizing factors in a medium of infinite msponding absorption spectrum are given in the Figure 4.28) . Thus negative polarization appears h ~ g l a r i r e d if the period of rotation is greater than the lifetime r. that is. ing bands and can help to resolve hidden transitions. the maximum polarization will be 0. -+ So in emission or S. i. since emission always occurs from + + is the sum of OP OQ = Il Ill. and hence the 6p~larization I of fluorescence. The inner curve (4.17B. A negative value for the degree of polarization 'Wmponent will change the relative orientation of the transition moment may be observed.

Thus. The fluorescence depolarization measurements have found application 0 a inbiochemical studies to measure the size of large molecules such as a Protein. if the polarization of a solution is measured as a function of tem- perature under conditions where lifetime 7 does not vary with temperature.33) 31 V P where. or mixtures of two solvents such as water and glycol to give a series of solutions 3f variable viscosity. the plot of I/p vs T/% should be linear. 1/3)/V. According to the theory developed by Smoluchowski and by Einstein.34) I On rearrangement and substitution. and may change in different solvents. Such plots known as Perrin's plots can be obtained at constant temperature by using solvents of similar chemical nature but of different viscosity. RT ( l / p . has been obtained by Perrin. by an angle Aa. By inserting sufficiently sort lifetime T for At in this equation. -__-_--. Another parameter characterizing the polarization state of luminescence . The usual method is to tag the molecule with afluorescent reagent through an isocyanate. The molar volume V . I if a spherical particle of radius r rotates in a liquid of viscosity q. is the molar volume and p = 31VIRT is the average ~ i o of d rotation or the rotational relaxation time. then the mean value of aagular rotation haa is dvcn by the Brownian equation for rotati~nalmotion: A Q= ~ --kT At 4z rsrl RT =-At=- ht (4. V = dxrs N. in a short time At. the observed degree of polarization p. FUKO-W OF pxOTOCHEMISmY I flSICAL PROPERTIES OF THE ELECTRONICALLY EXCITED MOLECULES 119 alld the radiative lifetime of the molecule. From the intercept. These tagged molecuies are known as JIuorescenr protein conjugates. Assuming a spherical shape. isothiocyanate or sulphonyl chloride group. Both these alternatives have been found useful in specific cases.35) giving a linear relationship between l / p and fluidity of the solvent medium. llp. which results from rotation of all the individual oscillators around statis- tically oriented axes. the molar volume can be calculated. we get 1 P -=-+(i-3)TT 1 Po 1 RT (4. for vertically polarized exciting light. and the - slope. The lifetimes Ofthe conjugates are usually close to those of the simple fluorescent mole- cubs. as 0 a" 2+ o q o n (i-i)=(i-!)(l+:) (4. An uncertainty is that here rl is the microscopic viscosity or the medium which may be diffcrcnt from macro- scopic viscosity. includes the solvation envelope -------. the lifetime r can be calculated if molar vol~ime V is known and molar volume can be calculated if T is known from other sources.

formaldehyde molecule The concentration depolarization is observed at a concentration < 10-3M has a planar geometry in the ground state. On the other hand. Feofilov is 4. The state. this effect is reduced if the lifetime 7 .. . liquid and solid behave alike. mound state but bent in their lowest excited states. acceptor molecule has a different orientation than the donor molecule. On I bl absorption of radiation it undergoes isomerization to all trans form and is Fiewe 4. The details of energy transfer given viscosity rl. R = i (3 cos2 p-1) (4.0 bond. An expression for reduced degree of polariza- tion due to self-depolarization is given by In tems'of angle f3 between absorption and emission oscillator. (A) Concentration depolarization Molecules such as CO2. Arrows detached from the protein..120 FUNDAMENTALS OF PHOTOCHEMISTRY pggYSICAL PROPERTIES OF THE ELECTRONICALLY EXCITED MOLECULES 121 radiation is the degree of anisotropy R.18) thereby completely losiilg its initial polarization direction.10. concentration in mol litre-' and Ro 4. As can be easily visualized from Figure 4. the emitted radiation will be depolarized.11 GEOMETRY OF SOME ELECTRONICALLY EXCITED MOLECULES where A is a constant and C. the chromophore snuggly fits into the conformation of the protein opsin. 2a is the molecular diameter. of the excited state is reduced. However. The . indicate the vector directions.18 Concentration depolarization by dipole-dipole mechanism. Free rotati011 in the excited state will lead to cis-trans isomeri- zation.19. If the \ rigidity of the molecule and it can now twist along the / C . HCN and acetylene are linear in their (B) Rotational depolarization. Such long-range energy transfer by dipole-dipole mechanism can lead to energy wandering from molecule to molecule until it is finally emitted (Figure 4. an electron localized on 0-atom is transferred to an anti-bonding reason for such depolarizing effect is dipole-dipole interaction between the x-MC) ~ h i c hhas 3 node bet\veen C and 0 bonds.empirical relationship found by Sveshnikov and mechanism will be taken up in Section 6.2 Concentration Depolarization is the critical distance between parallel dipoles at which the probability of is equal to the probability of energy transfer. defined as depolarizatiOn is independent of viscosity of the medium. in which changes in the geometry of retinal consequent upon light absorption. This destroys the neighbouring molecules whereby electronic excitation energy is transferred from initially excited molecule to its neighbour at fairly large distances. C. In the 1I-cis configuration. A similar situation is possible for conjugated systems like ethylene or butadiene. On excitation to the l(n. CS. 1 9 Ground state and excited state geomctr) of formaldehyde molecule. can trigger a series of reactions.6.37) where. Such polarization A further depolarizing factor is introduced in concentrated solutions of: studies can be used to calculate R. concentration of the solution. x ) where molecules are apart by an average distance of 7 nm or more. a phenomenon which is utilized by nature for reversible processes like vision. The concentration depolarization or self- Emission Figure 4 .

13 STUDY OF EXCITED STATES BY FLASH PHBTOLYSIS transition state for reactants '4 and B with spins SA and SB can be obtained EXPEHIMEhTS A h D LASER BEAMS by vector addition rule as I SA 1 SBj. A + ( tBf ) * (singlet + triplet*) tl-4 + t (doublet + doublet) f f + 4 3. The N'igner spin rule is utilized to predict the outcome of the transfer occurs between an excited atom or a molecule and another photophysical processes such as.. allowed electronic states of triplet-triplet ~noleculein its groundstate or in the excited state..spit1 c. Such reactions rates (Section 10.J.3) and laser sources (Section 10.f 4 (doublet + doublet + singlet) (f t-lt)' triplet* Triplet-triplet (f?)* + (t . 7 ) the following combinations are possible : variation for a single and a double bonded system is given in Figure 4. molecule are bent in their @em remains the same. The triplet-triplet absorption. Thus..Tt4 + -l doublet + doublet ti. . Wigner's rule states that the total spins of the a type ( f ) State. electronic energy between the energy states of the same molecule also.atioir reactions. 2 0 Variation of potential energy function for ground and excited (.HCO. state.il ' p bond i E thylene) ttt +f quartet + doublet Figure 4 .+ : 4 singlet + singlet 4. we expect different products for singlet-sensitized and triplet-sensitized nrk.)* (J. ( S Af SB-] 1.12 U'IGNER'S SPIN CONSERVATION RULE These rules also predict the nature of photoproducts expected in a metal- In any allowed electronic energy transfer process. Such transfer of energy by exchange mechanism (Section 6 6 . quenching by paramagnetic ions. etc.. (triplet + doublet + doublet) f + f -1.T)B -fJ. In these reactions a close approach of two reacting partners is necessary.&Hz. From the restrictions imposed by conservation of angular momentum of the system should not change.. no matter how we combine them in the final ground state but linear in their lowest excited stares.t. ~ ~ l t i y l i c i l i cofs initial state Multiplicities offitla1 state singlet-singlet (. The possible spin of the 4. doublet S ~ n g l ebond ( 8~phenyl) Di. the transition The study of the short-lived excited states is limited by the low concen- state formed by the products must also have total spin magnitude which trations in which they are created on excitation with normal light sources.t-+t+ t triplet + doublet 4. can be effectively measured because of high concelltrations of the .2) have helped in the whether physical or chemical. triplet lifetime.F.$)* + ( T 4) + ( f 1) ( t J)* singlet + singlet Ti?+ 4 doublet + doublet + * 4 t 2. Study of the triplet states of molecules. Wigner's spin conservation rule requires that there must be correlatioll of spins between the reactants and the products. and possibly NO. are known as adinbatic. But the phenorneno~lis governed by rules for dipole-dipole interaction primary processes leading t o reactant-product correlation.1.r~.f)* t. for example. j singlet + doublet + doublet Triplet-singlet (??I* A + (4. irlt ersystem crossing rates from triplet t o ground singlet Essentially. In order that there is smooth correlation with the products X and Y. spin is necessarily conser. triplet-triplet and triplet- Those molecules which change their geometry in the excited state s h o ~ a variation in their potential energy function with the angle of twist. belongs t o one of the above values. In an electronic transilio~l annihilation processes. the overall spin sensitized reactions. transfer by exchance mechanism and also in a variety of photochemical ved. (tl.20. in singlet-singlet.122 FUNDAMENTALS OF PHOTOCHEMISTRY p ~ Y S I C A L PROPERTIES OF THE ELECTRONICALLY EXCITED MOLECULES 123 and the B type (4 ) in the combined initial and the final states of the radicals such as . The rule is applicable whether known as Wigirrr's . . This situation allows the reactants and The use of high intensity sources such as Rash lamps with suitable flashing the products to lie on the same potential energy surface. This statement is spin. ISA-SB/.otls~.ttt)* quintet* states of biphenyl (single bond) and ethylene (double bond).)* .

Geometry of the molecules may change o n excitation with an important effect on excitation. cycle may be used to determine A p K ( = p K f . The relationship is obtained from Onsager's theory of reaction field in solution. By using high intensity flash lamps and laser sources. function of intcrnuclear distances is represented in the form of potential energy 11. state. the Franck-Condon from the instant of absorption to the instant of emission. T-T annihilation energetics and other photophysical dipole moments and polarizabilities in the two states may be different. When excited with plane polarized light. and physical behaviours as compared to the normal ground state molecule. 14. If the energy of promotion is greater than the dissociation energy of the molecule. causing blue-shift or red-shift in the absorption chemical properties of the triplet states can be studied. . Summary aldehydes and ketones with lowest l(n. xf and x]' are. Wigner's spin conservation rules govern energy transfer between two molecules. r. Solute-solvent interactions are of two types: (1) uniJersal interaction. Triplet state constants p ~ areT closer t o those for the ground state. A plot of . weak emission from upper energy states. Electronic &ransition\ between two energy states are governed by the Franck.. p. can be calculated from the relationship between the tional excitation is coupled with electronic excitation and gives rise to structure degree of polarization and the viscosity of the medium from the expression. and v" in the initial electronl: a higher energy state the degree of polarization may be negative. the degree. has been observed for many systems other than azulene. oC polarization p.cSo transition. Using high intensity laser sources. Such interactions are van der Waals type. Specific interactions are short range interactions and involve H-bonding. The potential energy as a in the ground state. the effect is viscosity .. Singlet excited state acid dissociation constants pK* can be smaller or greater with picosecond (10-l2 s) laser light pulses. 6 .r. Phenols. of varying orientations are exposed to plane polarized incident radiat~on. Polari~ation data can help to assign the transition moment direction in an 4. and (iii) increase in concentration. For polyatonlic radiation from a n anisotropic oscillator can be depolarized due to a number of molecules. overlap integral J xf xi d. 10. (ii) Brownian motion of rotation which changes the transition moment direction Condon principle. state dipole moment. is important. 12. It depends o n the dielectric constant D and refractive index n of the solvent and the dipole moment p of the solute mole- cule. Variation in intermolecular force constants are reflected in potential energy electrochemical gradients. Universal interaction is due to the collective influcnce of the solvent as a dielectric medium. Redox reactions can be initiated on electronic excitation against the 2. higher than the first. than the ground state constant pK by as much as 8 units. In quantum mechanical terminology. inground state and excited statedipole moments are manifested in differences 15. H-bonding ability may change on excitation specially for n+r* transitions. photophysical and photo- in solute-solvent interactions. with an efficiency N lo-'. In general. 7 . PHYSICAL PROPERTIES OF THE ELECTRONICALLY EXCITED MOLECULES 125 triplets generated thereby and because of their long lifetimci. the photodissociation energetics. Phosphorescence spectra are shifted at still longer wavelengths and the photochemistry of the molecule. factors: (i) random distribution of molecules such that transition moments they cannot be quantitatively obtained in practice. These sources also help and emission spectra. Excited state redox potentials may be different from those of the ground state Molecular geometries and internuclear force constants also change. Differences and photochemical processes. d o not obey the mirror image relationship with S.. Due to differences in charge distribution in the various energy states of a mole. is found to emit from the first singlet and triplet states following excitation 9. vibra. If excited to wave functions for v' in the final electronic state. charge-transfer or exciplex formation. in the absorption spectra. Due to differences in charge distribution in the ground and the excited states. FBrster's 1. of emitted (PE) diagrams in two dimensions for diatomic molecules. Emission also follows the Franck-Condon principle. Fluorescence spectrum may appear as mirror image of absorption towards the longer wavelength region for If r is known. Azulene which is known to emit from the second singlet state. respectively. t o study emission from upper excited state. upper PE curve with respect t o the ground state PE curve. The shapes of the absorption spectra depend on the shape and disposition of the absorption band. 3 . A negative slope is obtained if p. The excited state lifetimes. a continuum is observed. thiols and aromatic amines are stronger acids upon excitation. large polyatotnic molecules whose equilibrium bond length d o not change On 13. Electron transfer in the excited state may be reversed curves of the various energy states of the molecule. values. the electronically excited species can be completely different in its chemical if proton transfer occurs within the lifetime of the excited molecule. 8. Both these gives a positive slope if excited state dipole moment p. whereas carboxylic acids. 5. T*) states become much more basic. < and are 0-0 energy in a b s o ~ p t i o nand emission respectively. vibration and temperature dependent. and (2) specific interaction.<p.p K ) from fluorescence measurements cule. An important example is photosynthesis in plants. the molar volume Vcan be calculated. is greater than ground factors are convenient for sequential biphotonic processes. polydimensional liypersurfaccs are mathematically r e q ~ i r e dalthough .

unless it gets involved in a photochemical reaction and loses its identity..So (5. liquids and solids. e.4 + heat Reverse intersystem crossing (ISC) T.. etc. molecules in triplet state and in the ground state respectively. But in condensed systems.10) A*+ B-t A + B * Electronically Excited Molecules L Electronic energy transfer (ET) (5.3) A* -+ A -t hvf Fluorescence emission S .11) A*. P = phosphoresence emission.6) 3A -+ .1. In radiationless processes such as internal conversion and intersystem crossing the excess energy is lost to the environment as thermal energy. SA and A are molecules in first excited singlet state.8) A* + A -+2A heat + Self-quenching (5. Some are intrinsic properties of the molecule arid are unirnolecular while some others depend on external perturbations and may involve bimolecular collisions.g.7) A* + S -+ A heat + I Solvent quenching (5. in polyatornic molecules and in gases at reasoilable pressures. -So (5. 5 ) 3A -+ . solutions. 1: = nth triplet energy state and vibronically excited state IC internal conversion.. All these photo- physical processes must occur in a time period less than the natural radiative lifetime of the molecule and priorities are established by their relative rate constants. ~HOTOPHYSICAL PROCESSES IN ELECTRONICALLY EXCITED MOLECULES 127 .9) Photophysical Pr~cessesin ~imolecular A* 4-Q -t A + Q f. there are more t h ~ none pathways available to the excited molecule for dissipation of excitational energy. heat Intersystem crossing (ISC) Sl Tl ( 5 .. ISC = intersystem crossing F = fluorescence emission. S.4) A* +3A _1. Radiative transitions are denoted 5. These different pathways are grouped under photophysical processes in electronically excited molecules.heat Impurity quenching (5. Some of the unimolecular processes are repre- sented by a Jablonski diagram in Figure 5. -.2) j + heat - A* A -a Internal co~lvcrsion(IC) S. the various photophysical processes that can occur in a molecule are: . 1 Jablooski diagram for photophysical pathways After the initial act of absorption. Figure 5 .A'*-+ A* + heat Internal convzrsion (IC) Sn~ hS1(5. In monatomic gases at low pressures and temperatures.t + Avp Phosphorescence emission TI -So (5. reverse transition with emission is likely to be the only mode of return. Sn. energy i n S. -+ So (5.1 TYPES OF PHOTOPHYSICAL PATHWAYS A molecule excited to a higher energy state must return to the ground state eventually.SL = nth singlet energy state and vibronically excited sta:c where A'* is either an electronically excited nolecule with excess vibrational - T. state or a molec~lleexcited to higher singlet states S.

can undergo various photophysical and photochemical processes according to its owrl charac- tronic energy of S. generating 3A + A* -+ A ~ V E D E-type delayed emission of fluorescence (5. S3.etc. Hence the short-lived direct In the T. k~ 1O1O S-l can compete with fluoresce~~ce emission. self-quenching.18) for intersystem crossing should also be 1012s-I but due to spin restriction + A* += A h v p ~ P-type delayed emission of factor. by radiative fluorescetzce (5. Once in the zero vibrational level of such as the first excited singlet state. a clear knowledge of various photophysical processes.13) and partly nonradiative pathways as represented in the Jablonski diagram. ssions have emission spectra identical with that of the normal fluorescence Hence it appears as delayed emission when the exciting light is shut but with longer radiative lifetime. In this process. We shall discuss well as in solution. each of these processes one by one. under special experimental conditions (high intensity fluorescence emission from the S. scence. A * + Q + A Q * Exciplex formation (5. the same as vibrational frequencies.This account keeping of the absorbed quanta. triplet-triplet absorption T. tran. (T2w-+ TI. state. 1 . -+ So. HC-~SOor partly radiative + AA* -t 2A h v ~ Excimer emission (5. S. a few other processes niiiy be initiated. w .t So processes. TI + So or by nonradiative reverse intersystem crossing. as compared to the same processes in higher energy states because of + 111.19) can effectively compete with fluorescence emission which can have a rate constant as high as lo9 s-l. The long life is due to the involvement off. states or. The second molecule. T + + T -+ A* A Triplet-triplet annihilation to excited singlet (5. or by added substances. 11.16) large energy gap between the two.nonradiative internal conversion. of the triplet state as a n intermediate. conv~rsion(IC). so to say. may help inhibit emission because frequency of bimolecular collisions in gases as modify a given chemical reaction if it is so desired.2 RADIATIONLESS TRANSITIONS-INTERNAL CONVERSION the solute nioleculos are bathed. T* heat + A* Thermal excitation of triplet to singlet (5. Solvent quenching may involve other physical parameters as well such as solute-solvent interactions.12) emisslofi S. it can be populated indirectly. reaction. Since the solvent acts as the medium in which 5. transfers its excitation energy by no~lradiative mechanism to another molecule which is transparent to this particular states Sq. Again due to spin restrictions. Bimolecular reactions such as quenching. The elec. involves nonradiative transition from singlet to triplet state.15) less.1012S-I) rather than These photophysical processes often decide the photochemical behaviour radiative return is predicted. or to higher vibrati~nallevels of the Sl state in a time period 10-15s ( k = 1 0 1 5 S-I) obeying Franck-Condon principle. S. Radiationless return to TI. Under certain conditions. S. A * + A + A A * Excimer formation in the absence of a photochemical reaction. that is. The rate constant of internal conversion is 5 I O I 3 --loL2 S-I. t TI Lewis in his early works. T.. excess vibrational energy of S.17) which can then decay by radiative phosphorescence emission. A molecule in the singlet state is a different competitive for internal conversion and intersystem crossing in the upper chemical species from that in the triplet state and may initiate different states. -+ So is difficult.fer (ET). either by molecules of the how the absorbed quantum is partitioned into different pathways is essen- same kind. for a complete understanding of a photochemical forbidden by selection rules. wavelength. impurity quenclzitlg. Thus. solvent quenching may be classified under AND INTERSYSTEM CROSSING unimolecular processes and a clear distinction between it and internal A polyatomic molecule in condensed system when excited to a higher conversion S. it varies from lo1' to lo7 s-I. the molecule may return to the ground state. a molecule initially excited by The initial act of absorption may promote a molecule to higher energy of radiation. E-type delayed fluorescence was called a-phosphorescence by by absorption of suitable radiation. thus excited. state is referred t o as prompt fluore- flash excitation) the molecule may be promoted to upper triplet state T. I.14) Internal conversions from S1 . although direct absorption from ground singlet to triplet is chemistry. phosphorescence The processes 111 and IV termed as E-type and P-type delayed emi- emission from the triplet state to the singlet state is a slower process. quickly lost to the surroundings by a mechanism known as intenlnl teristics. += Sowhereas nonradiative processes by wavy arrows A very important bimolecular deactivation process is the electronic s1*-t so. Both the above radiationless processes fluorescence (5. Rate constant IV. Intersystem crossing (ISC). --+TI.128 PUNDAME~TALS OF PHOTOCHEMISTRY p f r ~ ~ ~ ~ H Y SPROCESSES ICA~ IN ELECTRONICALLY EXCITED MOLECULES 129 by straight arrows S. k e 1013. .-tSo have smaller rate constants lo8 s-' or + + AQ* + A Q ~ V E C Exciplex emission (5. state i. Higher triplets can also be populatid by of a molecule and reduce the quantum yield of a photochemical reaction intersystem crossing (ISC) from higher singlet states if rate constants are to much less than unity. Therefore.

the two energy states are coupled by the photon or the radiation is known as intersystem crossing. the dipole nzomrnt opcrator . Due to large energy gaps. if Yft and Yf are wave functions of two combining (iia) S. krsc r 10' -lo-' S-' s b . and Siebrand and has been property of polyatomic molecules. In the theory of non- folds S j -+ Tk or Tk -+Sp. the probabi- ~ t of y energy transfer between these two states is: 5. In a polyatomic molecule with 3N-6 modes of vibrations such the observation that internal conversion occurs also in individual polyatomic loss in energy is observed even in the vapour phase at very low pressures molecules such as benzene.. further improved by Bixon and Jortner for isolated molecules.-tSo. transition from S. It is unity when the spin functior~sof point of equal energy for both the curves. conversion is so called because the nonradiative loss of energy occurs In the theory of radiative transition. Even if the excitation is to an energy state higher than Zero-p~intlevel of higher electronic energy state to the high vibrational S. the initial and the final. krCe 1013. The transfer occurs irreversibl) l* two states arc the same. In these radiationless processes. But this theory is inconsistent with energy. the two states are coupled by an operator called the From kinetic considerations each can be further subdivided according C- to observed values of rate constants: kIc. crossing. This radiationless cascade of energy is known a. but the Thus. radiative transition. In the radiative transfer. and (ii) intersystem crossing. or (ii) to cross ovrr to the lowest triplet state non- radiatively. . Hence. the coupling is brought about by the environment acts as a heat sink for dissipation of extra energy as thermal phonon field of the crystalline matrix. The second is merely vibrational relaxation. klsc a: 10". The internal subject is still imperfectly understood. Otherwise it is zero but may have nonzero .. are the configuration spaces for electronic. and (ii) the rapid loss of excess vibra- first excited state S.lo6 S-' (iib) TI .. . -St. In such cases the medium does not actively where collision frequencies are likely to be less than the rates for radiation- participate except as a heat sink. which is the first term in the above expression. The operator ?N is effective on Born- (ib) S . the time for a tional manifold Thus.1 Theory of Radiationless Transitions Radiationless transition between two electronic states may be represented as occurring at the point of intersection of potential energy surfaces. p m ~ H Y S I C A LPROCESSES IN ELECTRONICALLY EXCITED MOLECULES 13 at this isoenergetic point to the high vibrational level of the lower energy vibrational level of the first excited state. to So is not and is of main interest. the rate constant for internal nuclear kinetic energy operator JN and the Franck-Condon overlap integral detennnes the probability of horizontal transfer between the potential conversion and kIsc. In an N-atomic molecule with 3N-6 modes of where d q . losing all its excess electronic and vibrational energy tional energy after transfer. always probable by radiationless mechanism. '. the molecule tt~inblesdown quickly to the zero vibrational level of tht. k l c E 108s-l or less O~penheimerstates only in which nuclear and electronic motions can be Separated. Under these circumstance^ various theories have been proposed for horizorztal transfir at the the molecule has two alternatives: (i) to return to the ground state by isoenergetic point. or p011lt5of near-crotsing amongst them. (ia) S j ~ . This nonradiative transfer from singlet excited to triplet state to explain it in the same way as the radiative mechanism. the field. This was take11 into consideration in less conversion. S j -4 Sk or T j -+ Tk. there are two major types of radiationless or nonradiative transi- tions: (i) internal conversion. the radiationless conversion of energy involves I H ~ O molecular vibration. The phenomenon is similar to the one encountered in predissociation spectra - of diatomic molecules. the rate constant for intersystem crossing. A crossing point is t h e R e last term is the spin integral.* h between electronic energy manifold of the same spin type: singlet-singlet or couples the two electronic energy states and the Franck-Condon overlap triplet-triplet. It follows that nonradiative conversion is an intrinric theories proposed by Robinson and Frosch. dry and dr.1012S-' functions of the two electronic states. The intersystem crossing involves integral determines the vertical transfer probabilifj*(JY/ Y i d T ) ~betwecn nonradiative energy loss between energy states of two different spin mani. the vibronic wave functions of the two states. v++ T. The-e will be many points of ~ h o n i wave c function only. loses its excess vibrational energ! state and the excess vibrational energy rapidly cascades down the vibra- to the surroundings in a time period r! 10-'3--1012s.-a- vibration there will be 3N-6 polydimensional hypersurfaces describing the tianal and spin motions respectively. In the nonradiative transfer. --t So. then under the perturbation 7. Gouterman considered a condensed system and tried fluorescence emission.2. steps:(i) the vertical transfer of energy at the isoenergetic point from the internal conversion. The first step is the rate determining step within 10-l2 s. level of the lower electronic state. The perturbation acts on tllc potential energy fiinctions for e3ch mode.

v" = 12. In this diagram.3. The transfer is further facilitated by momentary freezing of the nuclear coordinates at the vibrational turning points."O states for horizontal transfer of energy.2a) because the higher vibrational the ground energy state So. The density of energy state QE is defined as the number of vibrational levels per unit interval (in em-l) at the energy of the initial state. Transfer occurs at the crossing points which are isoenergetic for the two combining states. etc. it is observed that since the initial state is at or near the zero-point lap integral. Since only the overlap regions need between higher energy states S.has level of S. v' = 4. and two upper electronic states Sl and S.2b). nonradiative transfer but due t o the difference in the densities of energy states in the initial and the final states. --t S. zero-vibrational bz considered. the overlap integrals for the two cases can be represented Energy difference between S. The overlap is good mainly because the wave functions have large values at the extrerna as expected from a classical description of harmonic oscillation.n-tS. the medium may provide a background of its own dispositions of PE surfaces of Sz and Sl states are such that the two curves states which are nearly degenerate and in resonance with the .132 FUNDAMENTALS OF PHOTOCHEMISTR~ ~HoTOPHYSICAL PROCeSSES IN ELECTRONICALLY EXCITED MOLECULES 133 value under spin-orbit coupling interactions. Symmetry restrictions and spin multiplicity rules i m ~ a theirs~ own inefficiency factors. and So is generally much larger than that g~ shown in the inset of Figure 5. the a rigid matrix.2).. there is always a possibility of potential energy surfaces crossing at some point. Sl and Sz and Franck-Condon Over. Sl and the nverse Sz.. A large overlap integral all potential and the probability function is large.S. the smaller will be the overlap integral and the smaller will be the transfer efficiency.e. which the energy is transferred is associated with high vibrational quantum '"umbers and hence have very closely spaced vibrational energy states as The two curves are nearly parallel and they overlap near the equilibriunl expected for an anharmonic oscillator. between the two combining states is large. and the Franck. we find that S. Condon integral is such a situation is likely to be obtained when the (0. 5. of a simple diatomic molecule (Figure 5.2. From Figure Figure 5. - The transfer is in general irreversible and is immediately followed by fast vibrational relaxation phenomenon. the two potential functions intersect (Figure 5. Since the higher energy states are closer in energy. Inset: (A) Overlap integral between s. 'The overlap integral is indicates a high transfer efficiency... (v' = 0) state can overlap only with a high vibrational level of very poor overlap integral (Figure 5. the energy levels are very sparsely spaced.2 Potential energy surface for So. Equation (5. enegry states of So have low probability distribution function in the centre. The irreversibility of transfer is not due t o any difference in the probabilities of forward S.'l2 and s:'' and of S. Sl. Therefore. Furthermore. The middle term defines the intersect at a point v = 0. .20) thus predicts low probability of internal conversion between S. For S. The large Franck-Condon integral is not always the sole criterion for efficient cross-over from one energy state to the other..lo-*. s. A qualitative understanding of the collcept can be obtained from the potential energy surfaces for a ground state S. in solution. It follows that the larger the energy gap between Sl and So states. by simple superposition principle. At the point of intersection the lower overlap criterion for vibrational wave functions of the two combining ~ u r v eis at the extreme position of vibrational oscillation where encrgy is states and is the familiar Franck-Condon integral." and s. This is the rate determining step and must occur before the molecule starts oscillating. and So states. pictorially. specially nuclear geometry where kinetic ehergy is large.0) energy gap d ~ . S. On the other hand. i. But the state to (B) S. within 10-l3 .

the thermally relaxed singlet state to the vibronically excited triplet state sitions in polyatoinic rpolecules. Azulenes and substituted azulenes are some state is isoenergetic with zero-point energy of the upper state. Solute-solvent interactions may further other molecules have been observed to emit very weak fluorescence. -t So fluorescence spaced energy levels which are in near resonance with vibrational levels also.I-- . transitions. * > 5 . state X interaction x overlap a complex molecule. The spin- states. The enlission is extremely weak. Therefore. It may provide many closely second flash fluorimetry have led to the observation of S. the final state is a quasicontinunm. that between Sl and So. In Further increase in the energy gap between the pure electronic states tends azulene.3 of density of energy states. whereas relaxation. state and is the mirror image of S. + S o various vibrational modes also increases. the permutation possibility of this energy in azulene originates from S. is large comparcd with to remove the system from the condition of resonance. FUNDAMENTALS OF PHOTOCHEMlSTRy (1) Density of states: p ~ the . initial state. This is followed by vibrational relaxation. The perturb the potential energy leading t o crossing of surfaces. . thereby promoting nonradiative Processes. between S. where AE is the 0-0 energy difference between S. But increase in A E can be helpful only to a limited extent. more sensitive measurement techniques such as pico- very clear. -So nonradiative transitions. if such a effect is controlled by the relative rate constants of the photophysical crosjing point was not present initially. Recently. the crystal fields may perturb the vibronic energy states enhancing orbital interaction modifies the transition rates. In condensed systems like solid crystalline Sj Tk ( j 2 k). It appears that in this molecule. A prohibition factor of the probability of radiationless transitions. S. But in the absence of specific solute-solvent interactions. Higher energy states of some for heat flow into the sink. The energy finds a large number of exit paths of varied vibrational modes but very few reentry paths. the energy gap AE. As a consequence.. factor factor factor The quasidegeneracy of the isoenergetic energy state E is described by Here p2 is the interaction energy between the two states. is the nth vibrational quantum number and v. hv.s. vibronic energy levels. (2) Energy gap A E between the interacting electrorlic states. The photochemical behaviour corresponding vibrational frequency in the final (lower electronic) state. This results in large transfer transition in absorption. The fluorescence from vibrational modes increase. certain restrictions are imposed for S. It includes inter- action with all the vibronic levels in the final state close t o the initially populated state and. and . To sum up. Figure 5. and S. These three factors are included in the expression derived by Robinson and l n ~ t ~ astate l F ~ n a lstare ~ r o s ~from h time-dependent perturbation theory. It certainly acts as a heat sink. of polyatomic molecules is almost always decided by the chemical properties Increase in A E implies t h a r a higher vibronic level of the lower electronic of their first excited state. therefore. the emission is normally observed from the zero vibrational level of the first n excited state of a molecule (Kasha's rule). and S. depends on the 0-0 energy gap AE. t So absorp- efficiency in the forward direction and large probability of vibratio~~al tion energy is lost in a time less than the fluorescence lifetime. cannot compete with fluorescence The role played by the medium in radiationless transitions is not yet emission. conversion from Sl but that from S. radiationless transitions are governed by the following - lo4 lo4 is introduced and the values of k I s c lie between 10" and lo7s-l. 2 Vibronic overlap or the Franck-Condon factor. The reverse transfer from the relaxed triplet to vibronically excited singlet three factors : is also possible. s2 (3) . for the nonradiative Rate of horizontal transfer from initial to finalstates as a function energy transfer or radiationless transition probability kNR per unit time. the The rate determining step in intersystem crossing is the transfer from medium probably has very little effect on the rates of radiationless tran.. The small value of AE facilitates radiationless the transfer probability decreases. where v. is density of electronic Franck-Condon impossible to collect it back to the initial high energy vibrational state of - . From the theories of unimolecular reactions we know that onco the energy is transferred t o different vibrational m ~ d e sit. Since the important exceptions to this rule observed so far. The energy These discussions provide an explanation for the fact that fluorescence E = 1 r.

This is due t o the differences in the zero-point The selection rules for radiationless transitions are just the opposite energy AEST between the combining singlet and triplet states which is of those for radiative transitions. therefore. -+ So) is as expected because on is in some cases.2 Selection Rule for Radiationless Transitions in certain molecules. Therefore. The ratio of the two rates may be as high as lo9 5. T N . Consequently.S o . 5. In some symmetric.-t T I . the molecule has a natural radiative lifetime. . AETs. x*) W+ 3(n. The lowest energy excited state is the TI state and is fairly long lived in In aromatic hydrocarbons. photochemical reactions. Even if the electronic transition promotes the molecule to an energy state higher than S. - In heteroaromatic systems.. There is a large difference in the rate constants krsc (Sl w+.9). (5.+ T . The sensitivity of cross-over rates on the energy gap is and forbidden transitions are: u ~ . (T.5. intersystem crossing is the k p . zero-point energy and vibrational energy differences are and repopulate the S. where A E s . All those factors which effectively alter the radiative lifetime are the same as those which cause variation in Wllator strength in absorption. --+ TIand Tl . n*) ~ .2.-.T I ) and kTSc (TI *+ So). Since direct excitation to a triplet state is a In these hydrocarbons perdeuteration reduces kFsc and consequently forbidden process by electric dipole mechanism. The formal explanation of such a depen- constants for these transfers are important parameters in photochemistry. to ISC IC transitions are : TI may in such cases proceed as S. ~is the g&g.3 FLUORESCENCE EMISSION The mechanism of fluorescence emission has been discussed in Section 4.w is again found to lie in the Franck-Condon overlap integral.. "ibronic state implying reduced FC factor. inversely related to the integrated absorption intensity as given by equation (3. In this State it has a lifetime governed by the transition probabilities of absorption. transitions are less probable and. The overall transfer S. . x*) states occur more readily if energy relationships are good. Therefore. energy gap is small. are slower processes as shown by El Sayed. u*+u and S . The nuclear kinetic operator ?N is normally much less than that between Tl and So. states andl(z.4. l(n. The symmetric aromatic molecules normally have symmetrical molecules another higher triplet state T. transitions between I(n.+ ~ ( x*) n . dence on AE. the molecule can gain thermal energy from the surrounding perdeuteration. z * ) w 3 ( n . is considerably reduced. the rate constant for phosphorescence emission. The rate demonstrated in Figure 5. x * ) 3 ( ~x*) .. The lifetime pathway by which the reactive triplet state of an organic molecule can be . subsequently emitting E-type delayed reduced.I36 FUNDAMENTALS OF PHOTOCHBMSTRY pfloTOPHYsICAL PROCESSES IN ELECTRONICALLY EXCITED MOLECULES 137 Of special interest are the transfers S. the cross-over point now lies at higher quantum fluorescence (Section 5. The reduction of kTsc (TI M-+ S. -+ So and Tl .S o . If S. the excess energy in Condensed systems is dissipated away to the surroundings as thermal energy and the molecule comes to stay in the lowest excited state.e. In the absence of any deactivating perturbations.24) controlling factor. is defined as log Figure 5 .T I y. 4 Plot of AET=-& YS log k G s for a number of aromatic hydrocarbons. . as it competes with radiative constant k .+ gSl. it is the favoured seat of to the ground state are dominated by CH stretching vibrational modes. allowed states.T . the radiationless transitions from the triplet the time scale of excitation process. x * ) and l(n. i. further reducing the energy gap A EST. Fluorescence emission is normally observed from the first excited singlet state of the molecule.) which populated under normal conditions. level. may intervene between S1 and TI ground state and antisymmetrical excited state. The rate constant for fluorescence m s s i o n k.97).. .

5). case for small unconjugated molecules sensitive method for quantitative jluorimetry. I \ . radiationless pathways are most thermally populated.of the exciting wavelength except when chemical changes absorbed quanta.303 E C1+ Dimrlhyl naphlheurhodine I' '. The intensity distribution in flu~rescencespectra is through 'rj. common deactivating mechanisms.. A fluorescence independent of the absorption wavelength as long as the emission occurs excitation spectrum is a more sensitive method of obtaining the absorption from the vibrationally relaxed upper state. Due to the working of the Franck-Condon principle and thermal ._. It is scence implies that the emitted quanta are of lower energy than the independent . concentration in moles per litre and I.30) Because of the independence of quantum efficiency on wavelength it is possible to obtain ajluorescence excitation spectrum which is defined and derived as follows : Intensity of fluorescence F varies as fractional light absorption I. when higher vibrational levels of the ground state are Section 5. will reflect the variation in e.2. e. is ~ defined as lifetime is much reduced and actual lifetime T J is 1 number of quanta emitted/s/cm2 ---I I (hvfl ~ 'rf = 4f = number of quanta absorbed/s/cm2 . ( 1 .. 5 Overlap region between absorption and emission spectra. I.. that is - F=4f +f Ia I.303~C1 (5. 4f 'rf = r (5. is incident light intensity. . 303 C1 can be expanded and 4f I. on elt~anol F = higher powers) = +f 102. Under certain conditions at occur but is lowered by competing deactivating processes as described in h ~ g htemperatures. the measured lifetime ~f is related to + f spectra (Figure 5. einstein s-l cm-a be unimolecular. as a function of wavelength Figure 5 . In condensed systems.1 + 2. E For small fractional absorption. Stokes' shift.28) intensity of absorption I.303eC') (5.n... (hv. .e.) may be observed.31) (5.F einstein s-I ~ m . Mirror image relationship of fluorescent species or a large background absorption.the intrinsic lifetime as '..33) it is also seen that for low fractional absorption. therefore. p~~TOPHYSICAL PROCESSES IN ELECTRONICALLY EXCITED MOLECULES 139 In the presence of other competitive deactivating processes.32) where + f is fluorescence quantum efficiency.rate of emission -- -kf -.. emphasizing the Boltzmann spectrum and is of great analytical value ia systems containing a number distribution of molecules in the emitting state.) kf t X--r where Eki is the rate constant for the ith competitive process. The fluorescence excitation spectrum should. or wavenumber. This red shift of the fluore. r. From equation (Levschin's rule) in fluorescence spectra is not observed if the excited (5.e-2. hvf < hv. there is an overlap region between absorption and emission reduce the radiative lifetime. (1 .] relaxation of vibrational modes. [SJ is the concentration of the lowest excited singlet molecules. anti-Stokes effect ( h v *~: hv. reproduce the absorption spectrum of the molecule. molar extinction coefficient. if F is measured as a function of Wavelength of exciting light of constant intensity I. thus providing a the.~ (5.33) Abs .*. C. optical path length. Since these deactivating processes also Generally. i. the average The quantilm eflcicncy of jluorescet~ccd .1. molar extinction coefficient. the fluorescence spectrum is always rate of absorpt~on I. the resulting variation in fluorescence intensity called fluorescence excitation spectrum. assumed to .[S. observed on the red side of the absorption spectrum.intensity of emission . % Since t$f is independent of wavelength. fluorescence state has very different geometry from that of the ground state as is usually intensity is directly proportional to concentration. in approximate niirror image relationship for polyatomic molecules.--.

In dilute solutions in water.OH. aniline is about 40 times more fluorescent than benzene whereas benzoic acid is nonfluorescent. (highly fluorescent) enhancing the nonradiative dissipative processes. of anthracene lies above - aniline the first singlet in anthracene crystal but below it i n the dissolved state. Fluorescence is generally observed in those organic molecules which have rigid framework and not many loosely coupled substituents through which vibronic energy can flow out. Hydrogen . In general. NH. /COOH -COOH :lectron withdrawing electron donating group vitamin A group (fluorescence 115 that of naphthalene) benzoic acid benzene (nonfluorescent) (fluorescent) Anthracene crystals are highly fluorescent (+f = 1.25).4 FLOURESCENCE AND STRUCTURE The classic example of influence of rigidity of a molecule on its capacity Although all molecules are capable of absorption. azobenzene is nonfluorescent. observed in large numbcr of compounds. These are: phenolphthalein (nonfluorescent) fluorescein (fluorescent) The rigidity introduced by 0-bridge in fluorescein makes the molecule highly fluorescent.0) but in dissolved a t e emission is much reduced (#/ = 0. Molecular adsorption on a substrate also enhances the fluorescence.g.. They are known as diazaphenanthrene is capable of fluorescence. On the other hand. e. acridine and acridine orange. which enhance the transition probability or intensity of colour. whereas Some substituents tend to enhance fluorescence. Following structures are called fluorophores in analogy with chrorno- phores and they are part of the molecules with conjugated system of double bonds. w o P H Y S I C A t PkOCESSES IN ~LECTRONICALLY EXCITED MOLECULES 141 5. fluoroclzromes in tbe same sense as auxochromes. electron-withdrawing substituents tend to diminish or inhibit fluorescence completely. Similarly. these are electron donors such as . fluorescence is not to fluoresce is found in the pair phenolphthalein and fluorescein. etc. A recent explanation of this large difference is that the second triplet state T. azobenzene (nonfluorescent) azaphenanthrene (fluorescent) acridine acridine orange (non fluorescent) (fluorescent) Naphthalene with same number of double bonds is nearly five times more fluorescent than vitamin A.

For this reason aromatic hydrocarbons are normally fluorescent. This Most organic fluorescent molecules contain conjugated system of double aplanation is substantiated by the fact that. Substituents which produce steric hindrance to planarity thus reducing x-electron mobility. fluoresce. In heteroaromatic molecules (x. Such structure x*) and '(n. x*) state as the emission wavelengths in the visible region. That is the reason why pyridine. polar solvents can bring about imparts certain rigidity to the molecule and shifts the absorption and the change in the order of the energy levels. making l(w. In Table 5. and a high fluorescence efficiency for such a system is (R-H. alcohol) (nonfluorescent) (fluorescent) . +CH=CH-CH=CH+ solvent. quinoline and acridine which are isoelectronic N-analogs of benzene. Some ortho hydroxy-benzophenones are used as energy systems. In Figure 5. x*) and (n. th: nature of this state will dictate the chemistry of the molecule. The rate constant for is observed to be large for dipole allowed x* -t x transitions. x*) as the lowest singlet excited state. x*) state is the lowest excited state. respectively. Any other process with high@ rate constant can compete with radiative transition and completely inhibit fluorescence radiation. cleavage energy 525 kJ mol-l 525 kJ mol-I (il. naphthalene and anthracene. benzene naphthalene anthracene. Heavy atom substituents tend to reduce the A (alcohol) n b m t n c e quantum yield 4. l(n. are nonfluorescent in hydrocarbon solvents. the relative quantum yields of fluorescence of quinoline in benzene. ~ Q ~ H Y S I C APROCESSES L IN ELECTRONICALLY EXCITED MOLECULES 143 Large energy separation between excited singlet S. because ofthe space forbidden character of this transition. Under these conditions predissociation is favoured. Since fluoresce~lce is generally observed from the lowest energy excited state of the same multiplicity as the ground state. dhanol and water are 1 : 30 : 1000. and triplet TI states bonding in some cases can activate fluorescence. n*) are not very far apart.1 are recorded experimental data for halogen substituted least stable bond Srphtha~enes. 4 diphenylbutadiene Substituents have considerable influence on emission characteristics of -matic compounds. max : 210 nm (1590 k1 mol-l) 350 nm (a336 kJ mol-'1 halogen series the effect increases in the order F < Cl c Br < I. CBHI7. xa) energy states have different emission probabilities. lower the fluorescence efficiency of the molecule. in others it helps to degrade favour fluorescence since intersystem crossing is less probable in such the energy. butadiene 1. etc. From the principle af microscopic reversibility it may be inferred that what is probable in absorption should also be probable in emission.g. For at higher energies than the strengths of their weakest bonds do not enample.=CH-CH= CH. the effect of polar solvent on energy h e l s of chlorophyll molecule is given. A high probability for (x. in favour of phosphorescence emission 4. Chlorophyll is fluorescent in polar CH. evidently due to such solvent effects the energy states. in those compounds in which bonds with extended x-orbitals in a planar cyclic structure. a consequence.6. degraders in plastic materials and printed clothes to protect them from puorescence efficiency increases with increase in the number of condensed damaging effects of sunlight.) usually observed. Linear ring systems are good fluorescers as compared to angular compounds like phenanthrene.CloHzl etc. All these compounds have I(n. If for a heterocyclic molecule. Me. The compounds which absorb lowest excited level with subsequent appearance of fluorescence. z*) state is predicted. other deactivating processes cannot compete with the o-hydroxy benzophenones radiative process. a longer life and hence a smaller rate constant for emission is expected. planarity of the ring is also an important criterion. < < e..

The external heavy atom perturbations fluorescent at room temperature. The paramagnetic susceptibility of the dye under this condition was found to correspond to a pair of electrons with prallel spins. . besides enhancement of S. quinoline and acridin-e. emit at longer wavelength with increased can bring about regular increase in the phosphoresccnce to fluorescence decay constant at liquid nitrogen temperature. 1 prevented and the molecule is able to emit. The transition probability can be enhanced by spin-orbit coupling interactions (Section 3 . 3 ) promoted by a number of techniques In dianions of xanthene dyes although halosubstituents decrease the described below.0023 conditions. state. emission is a rule rather than exception. quantum efficiency of fluorescence. i. Identity of the phosphorescent state with the state was conclusively established by them for acid fluorescein dye in boric acid glass. This increase is due to an increase in spin-orbit coupling when the n-electrons of naphthalene penetrate near the large nuclear field of the iodine atom. hence a long radiative lifetime. From this level it can return to the Naphthalene 0.4 intersystem crossing to the higher vibrational level of So with fast dissipation 31360 20700 0. halogen substituent in the solvent. using high intensity excitation source. -+ So nonradiative transition is promoted by heavy atom iodide. cm-1 r~ vibration level of the triplet state. cm-1 vP. rescence has a low probability of emission. 7 . The transition TI c So 1-Bromonaphthalene 6.2 always at a longer wavelength than fluorescence. 77 K.5 ground state either by phosphorescence emission (radiative pathway) or by 1-Fluoronaphthalene 0. although non. This metastable state was later identified with the triplet state by Lewis and his associates.068 31600 21 150 1. 6 Energy levels of chlorophyll a in polar and nonpolar solvents.01 4 is forbidden by spin selection rule and is not observed under ordinary I-1odonaphthalene > 1000 not observed 20500 0. by nonradiative mechanism. W+ T. It was first ratio for naphthalene on going to solvents with more and heavier atoms suggested by Jablonski that the emitting energy state for this longwave (Figure 3. Because of spin forbidden character. It (i) External heavy atom perturbation.23 of excess vibrational energy (nonradiative pathway).5 TRIPLET STATES AND PHOSPHORESCENCE EMISSION The intensity of the transition increases with the atomic number of the The heterocyclics pyridine. . A triplet state with unpaired spin should have residual magnetic field. The effect was first discovered is suggested that in these dyes. PHm~PHYSICAL PROCESSES IN ELECTRONICALLY EXCITED MOLECULES 145 144 FUNDAMENTALS OF PHOTOCHEMISTRY Hlgher energy states component is a metastablestate lying just below the singlet S. increase in the absorption intensity of the TI t So transition. S. phosphorescence efficiency is not incre- ased proportionately. each colourless alone.e. At low temperature and in Effect of halosubstitution upon emission characteristics of naphthalene rigid solvents.4 3 1280 20650 0. intersystem by Kasha who observed that a mixture of 1-chlornnaphthalene and ethyl crossing rates. is yellow and that the colour is due to an substitution. After crossing over to the triplet energy state at the isoenergetic point .8). all deactivating collisions are TABLE 5 . A large number of molecules were transferred to the triplet state via intersystem crossing from the initially excited singlet. The appearance of phosphorescence in the above mentioned heterocyclic compounds at low temperature implies that the triplet state homes populated by intersystem crossing from the thermally equilibrated lowest excited singlet state. Phosphorescence is 1-Chloronaphthalene 5. phospho- Figure 5 . Nonappearance of any emission at room temperature suggests that phosphorescence is inhibited by competitive nonradiative processes such as impurity quenching or internal conversion Polar spluenl Orv nonpolal solvenl to the singlet ground state. the n~olecule quickly relaxes to the zero Compound 'p'df vf.093 31750 21250 2. 5. The phosphorescence lifetime decreases with #f. In rigid glassy deoxygenated solutions.

The singlet and triplet states have different energies because of the electron-electron repulsion in the triplet state. -+ S. and the excited electronic configurations are delinked and singlet and triplet states are possible. is the rate constant for intersystem crossing from triplet to p u n d singlet. [TI]1. Because of the forbidden nat U Ie of T. In such cases: The phosphorescence lifetimes may vary from 10" second to more than If a quantum etliciency less than unity is observed. '? tr~plet.146 FUNDAMENTALS OF PHOTOCHEMISTRY t90~pHYSICAL PROCESSES IN ELECTRONICALLY EXCITED MOLECULEY 147 (ii) A second way in which singlet-triplzt transitions can be enhanced is through the presence of paramagnetic molecules such as oxygen and nitric for a few cases. The system crossing efficiency +rsc. the quantum efficiencies of fluorescence and phosphorescence in low temperature glasses (Appendix 11) such as EPA (ether : isopentane : ethyl alcohol in the ratio 2 : 2 : 5) add up to unity. a photochemical reaction. for phosphorescence emission and the actual lifetime substrate is saturated with 0. respectively. As a result phosphorescence is not observed at room temperature except .c So transition where 4s are the electronic orbital wave functions and Jls are the state .6 EMISSION PROPERTY AND THE ELECTRONIC If the lower eflergy state intersects at a point (Figure 5. transition.1) above the CONFIGURATION zero vibrational level of the transferring state.rate of phosphorescence rate of absorption _ ---k. is long lived and subjected to rapid collisional deactivation and thermal relaxation. k very low probability.2. For aromatic hydrocarbons. This suggests that direct nonradiative decay from S1 -+ So is of Hence.P einstein s-I . On electronic excitation. -- Tp a k p = kp/fa . a temperature dependent factor e-wlkT may be involved in the rate constant for intersystem crossing. T. It follows that the rate determining step.hv or 3+* nurnbeTper s e c o n d 3 quanta absorbedin-S. even in the absence of a second.1). Evans has shown that T. transition and +I -.36) from the exchange integral intensity of absorption 1. is defined as number per second of quanta emitted as phosphorescence in Or = T. c S. So via W+ higher vibrational level of the ground state is proposed. The intrinsic lifetime of triplet TI state sP0. einstein s-I [TI] is the concentration of the triplet molecules. the ground the molecule from the zero point to the point of intersection. The ground states of most molecules are singlet and contain a pair of The energy term W corresponds t o the activation energy needed to raise electrons with antiparallel spins. Exciplex formation is probably involved. The sequence of transfers is: where k. c So transition of a large number of solutions. (5. The quantum yield of phosphorescence. All the nonradiative paths t o the ground state are rOp kp + kTsC (kp k ~ ~ ~ ) / $7 i. 4. and +T are quantum efficiencies of phosphorescence emission and triplet formation respectively. The enhancerne~lt is the reciprocal of the sum of all the steps which dextivate tne observed in the presence of oxygen disappears when oxygen is removed. 5.. subsequent thermal equilibration is much faster (Section 5. It is observed at low temperatures only in rigid glassy oxide. is the reciprocal of the organic molecules can be observed if a concentrated solution of tile zate constant k p . a direct internal conversion from S.intensity of phosohorescence emission . The exterit of singlet-triplet split will be governed by the interaction enzrgy as computed . +T is identical with inter- where TI and S: arc vibrationally excited Tl and So state. 4. la- coupled via the triplet state. assuming that all those molecules which coupling transition in the horizontal direction at the isoenergetic point is do not fluoresce are transferred to the triplet state. at higher pressures. functions.

This explains the absence of room temperature emission in heterocyclics like benzophenone. x*) 1s the lowest excited SI state and energy gap between l ( x .* by a factor of ten. 19681 observed ai low temperatures it1 suitable solvent mediunl bpecially when S. the larger the overlap.x * ) and (. n*) aad (n.. ( c) A small value of A E ~ Tfacilitates intersystem crossing.8 for a few representative molecule types. short-lived I(?. the greater in the value of K. n*) singlet and triplet energy statcs come true if a higher triplet state T. iitghly tinprobable these factors are conducive to fluorescence emission and in general aromatic !e) ( f) hydrocarbons are good fluoresctr. We expect singlet state t o be fast depleted along this pathway if the lowest excited state is of (n. Both Q u ~ n o l ~ n ephenaz~ne .148 FUNDAMENTALS OF P H O T O C H E M I ~ ~ This is equivalent to coulombic repulsional interaction between two equal charge densities (++*e). Fluorescence with decreased rate constant for emission cannot compete efficiently with intersystem crossing. Horrocks in E. This pathway is further promoted due to the fact that T. hence the energy separation hEsT betweenl(n. 7 Splitting of singlet and triplet energy states of (n. In general. n*) and 3(n. x and x* orbitals occupy inore or less the same configuration space. Bowen (ed).x*) states is large. n and n* orbitals d o not overlap much as they lie in orthogonal planes. and T. i n n .7). In aromatic hydrocarbons.. quinolintt. Luminircence in Chetnistry. Sometimes. The value of I( depends on the overlap between 4 and +*. Large interactions result in relatively large LIEsr. I n such case\.+ X* transitions.J. diaztnes (a) (b) Figure 5 . For example. x * ) is small. 8 Disposition of (n. On the other hand. Qulnoline In hydroxylic Some possible dispositions of (n. x*) states are given in Figure solvents 5. n*) and (n. IS available near the S. They phosphoresce at low temperatures only. Aromatic cdrbonyls. acetophenone.R. Wilkinson and A. acridines. [F. x*) and 3(si. the singlet and triplet states will fall in the following order (Figb~e 5. fluorescence and phosphorescetxce both are characteristics. 2 . . the prediction may Figure 5 . z*) character. The S T energy split AEsr is equal to 2K. etc.*> T~. D. due to the forbidden character of n -+ x* transition. Some data correlating 4 E s ~and dqsc are given in the Table 5 . Van Norstand. state such as for a few repiesentative types of molecules and their emission in anthracene. x*) type. are states of diEerent symmetry type.x.

2 5. + heat Intersystem crossing k1sc LSll a. Even the nature of photoproducts may be different if these parameters change due to some An thraccne perturbations.] = (kTsc +k ~ [TI? ) diradical. and Because of their unpairedspin. etc. from ( 5 . + k ~ c krsc + kf apart that they do not interact. . *Triplet states are very important in photochemistry because they have longer lifetime and at the same time more energy than the ground state.150 FUNDAMENTALS OF PHOTOCHEMISTRY ~ ~ T O P H P S I C APROCESSES L IN ELECTRICALLY EXCITED MOLECULES 131 TABLE 5 . For example. from definition. The relative levels of excited states are sensitive to solvent polarity. the energy levels and thereby completely change the relative rate constants Under the condition of photostationary equilibrium. kf state may behave as a diradical if the electron charge densities are so far Similarly fer (TI) 1. Hence the quantum yield of fluorescence +.99 S. On the other hand. The spatial charge densities in a diradicai . x * ) state which may not T. Any of these factors may alter the relative ordering of excited singlet and triplet molecules. substi. they are likened with diradicals. the quantum yield for phosphorescence 4. = k----- f [St1 . hydrogen bonding.3 krc Benzophcnone Biacetyl 21 ( 5 ) 25 (6) 1 . rate of formation of S. Excitation 1.. = rate of deactivation of S. of various photophysical and photochemical processes.O 0. - Rate constants of unimolecular processes can be obtained from spectral Compound (nu*)states A EST X J mol-1 +ISC data and are useful parameters in photochemical kinetics. a*) states So + hv ko ---+ S. t Hence. respectively. the following reaction steps are important in deactivating the Naphthalene excited molecule back to the ground state. Ks are respective rate constants and [S. protonation in excited state. The seats of unpaired spins for anthracene and acetone triplets md on substituting for S. -a So + heat Internal conversion krc IS.] and [Tl] arc concentrations of tuent effects.32 S.7 PHOTOPHYSICAL KINETICS OF UNIMOLECULAR Singlet-triplet splitting AEsT and +. hence the photo. 3 5 ) and (5. A diradical and a triplet molecule may not always mean the same thing.28) in the triplet of a long conjugated molecule the electron density is deloca- lized and it cannot be identified as a diradical. kf S1 -+ So + hvf Fluorescence k f [SI] It has been pointed out by El Sayed that intersystem crossing is more k. Phenantbrene 'Iriphenylenc Step Rate (n. x * ) and (n. + SO heat Reverse intersystem kiC [TI] crossing be the lowest triplet. chemistry of the molecule. n * ) states PROCESSES . T. x * ) to 3 ( x . in the absence of any external quenching is. In the absence of bimolecular quenchingand photochemical Benzene reactions. (5. k&C High value of kSC in benzophenone is explained as due to the possibility of nonradiative transition from I(n. + hvp - TI ---+ So Phosphorescence k~ [TI] efficient if two neighbouring states are of different electronic configuration. -.45) is given as . 1 krsc Quinoline 122 (29) 0. The quantities in parentheses are AEsT in k caf mol-1.sc for ( x . - and a triplet molecule are different although the latter may behave like a klsc [S. a 4. are illustrated below.

2 Phosphorescence Phosphore~cence +. for benzene at 773C u 0.and $0 4.3 The value of k.. .. is reasonable. In this expression. In Table 5. For example: + -- (i) If 4... Relation to rate Observable Symbol constant Source Example Fluorescence. 4 j and rfo. k. = ( phosphorescence decay Gction that decayed<diativcly TABLE 5. their symbols. for fraction that decayed nonradiatively to rate constants and sources of studies are summarized. respectively. +. be obtained by making certain . f' + -- 1 may not hold. . relation rate const. and k p is obtained from the measured decay rates for phosphorescence at 77K in EPA.P #. can be obtained experimentally from the integrated area under the absorption curve Therefore. quantum yield Spectrum 1 1 k. is large and 4.2). the condition #..f) + (5..T.(#.T.2 3. = 0. The quantum yield for intersystem crossing is expressed as . +r 1. and kp. Fluorescence Calculation of radiationles: transition probabilities in benzene: quantum yield spectrum +.approximations. kf and k.39)) Singlet radiative (i) Absorption lifetime spectrum (ii) t Rate constants for nonradiative steps are difficult to obtain experi- mentally. are reciprocals of the radiati4 and lifetimes of flubrescene and phosphorescence states. Observable photophysical parameters. 5 x 10-2 s-1 (calculated from phosphorescence decay decay and eq.3 the observed quantities. then k.+So +is neglected but k.50) (Section 10. .=---- Fluorescence 7N %fU Singlet lifetime decay = 2 x 10s s-1 (calculated from integrated area under the absorption spectrum) Triplet lifetime Phosphorescence k. The ratio of the two emission efficienciesis then and the quantum yield for nonradiative decay of triplet There are established techniques for the determination of #. their relationship to rate constants Furthermore. since of various photophysical processes and sources of their information. FUNDAMENTALS OF PHOTOCHEMISTR~ "WOFHYSIEAL PROCESSES IN ELECTRONICALLY EXCITED MOLECULES 153 limiting value of k1sc can. 4 kp and in equation > If kIsc (kIc+ kf ) as is generally the case for many organic compounds. 4. (ii) If internal conversion S. (5. jn actual practice. the intrinsic phosphorescence efficiencyis given by This can give an estimate of krsc from the knowledge of 4. 3 . can now be calculated from the knowledge of +f.sc = 1 . however. specially heteroaromatic hydrocarbons.

154 FWNDAMENTALS OF PHOTOCHEMISTRY p)lb~OPHYS:2AL PROCESSES IN ELECTRONICALLY EXCITED bIOLECULES 155

The rate constants for unimolecular photophysical processes in few under den tical experimental conditions such as geometry of
representative organic molecules are given in the Table 5.4. These give experiincntal set up and optical densitieb of two solutions (Section
an idea of the order of magnitude expected for various processes.

TABLE 5 . 4
, 10.2).
actcal radiative lifetime = 'cfO (equation 5.30).

Rate constants for unimolecl?larphotophysical processes in some organic moleculec
4; : quantum efficiency of phosphorescence emission measured at 77K
In EPA solvent wing a phosphorinleter.

Compound +r 4~ kf k ~ a k&cb hsc c
,: : intrinsic lifetime of phosphorescence emission; on the assumption
that a11 the deactivation occurs radiatively either from singlet or from
at 77 K at 77 K 1G-6 s-1 s-1 s-1 s-1 triplet states, natural phosphorescence lifetime
Naphthalene - 1-br
- 'rP - (equation 5.39)
l-Chloranaphthalene C P

1-Bromonaphthalene q: lifetime measured from phosphorescence decay curve.
k,: rate constant for fluorescence emission = I/$.
I-Iodonaphthalene
kp: rate constant for phosphorescence emission
Benzophenone
Acetophenone
1 -
-- - - 4,
1 -

Biacetyl kIsc: rate constant for intersystem crossing S, -+ TI
Quinoline 1 -4f (equation 5.52)
df
a calculated from expression k , -
7;
=. '(
-
'9
--' W
1 - 91
);equations (5.39) and ( 5 . 3 7 ) k&c : rnte constant for intersystem crossing T, w-t So
b calculated from equation (5.52). k, - "P + ") (equation 5.53)
c calculated from equation (5.53). bP
The state diagram for biacetyl is presented in Figure 5.9 where
Esr -- 259.6 kJ molt1 and ET, = 234.4 kJ mol-l.
5.8 STATE DIAGRAMS
All the information collected from spectroscopic data such as energies,
lifetimes and populations of the S, and TI states can be incorprorated in
the construction of a Jablonski type state diagram for a molecule. Such
a diagram can be of immense help in predicting the photochemical
behaviour of a molecule.
The energy difference between the ground and the first excited levels
S, can be obtained from the 0-0 band in absorption and/or fluorescence.
The 0-0frequency in fluorescence is a better measure. For a T, state,
the 0-0 band o r the blue edge of the phosphorescence spectrum is
considered. Other parameters are :
7; .
intrinsic radiative lifetime; from integrated absorption intensity using
the formula given in Section 3.9.
47 : intrinsic fluorescence quantum yield; from integrated fluorescence
spectrum of a dilute solution expressed as number of quanta emitted
per unit wavenumber vs wavenumber. It is compared with a
standard of known +,
under equal light absorption. A simple way
is t o measure integiated fluorescence of the sample and the standard
F igure 5 . 9 Slate diagram for biacetyl.

@oTOPHYSICAL PROCESSES IN ELECTRONICALLY EXCITED MOLECULES
151
Whether the singlet is a (x, x * ) state or an (n, x " ) state can be
established from solvent effect. A blue shift in polar solvent suggests an
(n, x*) state, a red shift a ( x , x*) state. A rough guess can be made from
the radiative lifetime for fluorescence which is of the order of s for
biacetyl. Hence, it appears that the lowest excited singlet is an S, (n, x*)
state. From dilute solution value of $/, we find that only 1%0f the
initially excited molecules are capable . of emission with a rate constant
1 x lo5 s-I = I!$. Therefore 99% of the molecules must be transferred
to the triplet state, assuming S, . ~ . -Sot do not occur. The rate constant for

--
intersystem crossing, kIsc is 2 x lo7 s-l. After fast (k 1012s-l) vibrational
relaxation, 25% of the molecules decay by phosphorescence emission,
4, = 0.25; k p r 1 . 2 x 102 s-l. The rest 75 "/, decay nonradiatively by
--
reverse intersystem crossing; kTsC 3 . 7 x 102s-I. Biacetyl, is an interest- Figure 5.10 Jablonski diagram for E-type delayed fluorescence.
ing molecule whose phosphorescence is observed even at room temperature
in aqueous solution.
IC n ISC
S: S, T:

5.9 DELAYED FLUORESCENCE
The long-livcd delayed emission as phosphorescence has spectral
characteristics very different from fluorescence. But there are delayed
emissions whose spectra coincide exactly with the prompt fluorescence
from the lowest singlet state, the only difference being in their lifetimes.
These processes are known as delayedfl~rorescelzce. Two most important
k Acxpl \c R l i
types of delayed fluorescence are: (A) E-type delayed fluorescence and Figure 5 . 1 1 E-type delayed fluorescence pathways indicating possibility
(B) P-type delayed fluorescence. of emission from each relaxed state.

(A) C-type hlofrecl ~ u o r t ~ ~ c c ist ~ observed
cc when the singlet-triplet where A is the frequency factor and A EST, the activation energy equal
energy gap AEsr is fairly small, as is the case for dye molecules. The to 0 - 0 difference between the singlet and the triplet level.This type
molecules, initidly excited to the singlet energy level, cross over to the of emission was first observed in deoxygenated solutions of eosin in
triplet level by intersystem crossing mechanism. After vibrational relasa- glycerol and ethanol at room temperature and hence it is designated as
tion, if AEsT is small, some of the molecules may be again promoted, wit11 E-type or cosi~zt j p r i n the early work of Lewis and Kasba, direct
the help of thermal energy from the surrounding, to the isoenergetic poil~t ~hosphorescence was called @-phosphorescence and E-type delayed
and cross back to the first excited singlet? subsequently returning to the fluorescence as a-phosphorescence.
ground state by radiative process S, -+So (Figure 5.10). The various The ratio of quantum yields 4, to $E, of pi~osphorescenceand E-type
stages in the process can bc expressed as given in Figure 5.11 indicating the delayed emissions respectively can be deduced as follows.
possibility of emission from each relaxed energy state. Vh. is the quantum yield of triplet formation, then
If rate constants are competitive, we expect the emission of pron1pt
fluorescence, phosphorescence and delayed fluorescence of euergy quanta = 4~ k,
livf, hv, and hv,, respectiiely. Although livf is equal to kv,,, the lifetime of
$,I
kp t /<LC ED + (5.55)
thermal excitation to the S, state, fluorescence will occur with usual
delayed fluorescence \\ill match the lifetime of triplet decay. The rate Ouorescenceefficiency 4., Therefore, the efficiency of delayed fluorescence
constant h,, for E-type delayed fluorescence is temperature dependent and Cen is given as
can be expressed as

kED= A exp (- A EsT/RT)

d 58 FUNDAMENTALS OF PHOTOCHEMISTR~ ')IJOTOPHYSICAL PROW-SSES IN ELECTRONICALLY EXCITED MOLECULES 159
Hence.
LED A
$ 6 -
A ~.
k~ = 4r k-
df --- P exp (-- A EsT/RT)
+‘J

The ratio of the intensities of the two bands in delayed emission in which Z k r represents the sum of all first order processes by whicla the
spectrum should thus be independent of the efficiency of triplet formation triplet state is depleted. At low light intemities triplet-triplet interaction
and of all triplet quenching processes. It should also be independent is less probable than the first order decay. Hence, under steady state
of the intensity of absorption I&. The rate of emission is then given a% conditions.
ED [TI where ED is temperature dependent.
An Arrhenius type plot of +ED/+p as a function of temperature will give
the value of the energy gap A E S ~The value thus obtained has been where is the lifetime of the triplet.
TT If the dissoziation of the inter-
found to agree with the singlet-triplet energy difference 42 kJ (10 kcal) mol-1 mediate X is also fast, then the rate controlling step is the formation of
obtained by direct spectroscopic methods for eosin in glycerol. X by triplet-triplet annihilation process. Hence, th- intensity IpD of P-type
delayed emission is given as:
(R) P-type delayedfluoresccncc is so called because it was first observed
in pyrene and phenanthrene solutions. In aromatic hydrocarbons singlet-
triplet splitting is large and therefore thermal activation to excited singlet
state at room temperature is not possible. The mechanism was first U IPD/I,, on transformation and substituting
since ~ P = for [T]Vrom
formulated by Parker and Hatchard based on the observation that the equation (5.59), we have,
intensity of cn~ission of the delayed fluorescence IpD was proportional to
the square of the itztmsily of absorption of the exciting light I,.
In the pyrene system, the intermediate X has been identified with an
excited dimer or excimer, since characteristic excimer emission is also
rate of emission
-- - 1; -
-
rate of absorption
- I, observed. The process of triplet-triplet anrlihilation then consists of
+PD = I, transfer of energy from one triplet to another to form excited dimeric
Since + f is independent of I,, the ratio of the intensity of P-type delayed species (S):, which dissociates into an excited and a ground state singlets:
emission to that of prompt fluorescence should show linear dependence
on the intensity of absorption. The square law dependence indicates the
T +T --+ (S):
I
-+ S,+ So
necessity of two photons for the act of delayed emission and is hence
known as biphotonic process. It has been observed in fluid solutions of
So + So +excirner
j.
I~VE
J.
So + J1~1'1)
delayed
many compounds and also in the vapour state. emission emission
Thz mechani. XI proposed for this biphotonic delayed emlsslon is that Tbe generation of an excited and a ground state singlets from two triplets
encounter between two triplet molecules gives rise to an intermediate is a spin allowed exchange mechanism:
species X, which subsequently dissociates into an excited and a
state singlet molecule. The excited singlet molecule finally relaxes by T(1.1.) -tT(J-C> So(tJ.1 SI ($1.)
-+ +
emission of rad~ation. The rate constant of emission is not that of Such bimolecular quenching reactions occur at diffusion controlled rates.
fluorescence but is governed by the rate of formation of triplet molecules. A probability P for reaction per encounter may be included. The rate
constant terms in (5.61) become
The various steps leading to emission process are:

So + S, -+ T I~+T
and $ro/+/ = Pkdrrf Ia (4r ~7 )2
T --+ So .C k~ [TI (5.63)
The intensity of P-type delayed fl~~orescence
should decay exponentially
T+T +X k x [TIP with a lifetime equal to o~le-lral/of that of phosphorescence. Since in
X -t Product kr [XI fluid solutions, phosphoresce~iceis much weaker than delayed fluorescencc,

Under favourable conditions. The variation in fluorescence ~ i e l dmay also also known as electrochemiluminescence (ECL). arise due to change in the viscosity of the medium with temperature. As a conse- media. state. Sj -Sk or triplet-triplet.A) varies as 1/T.. whereas a radical anion has an electron system crossing is expected and fluorescence yield \?. Evidently cross-over point lies aboke Sly-O. is nearly unaffected. rescence should be independent of temperature. &ereas T. the A temperature dependent intersystem crossing rate will be obtained radical anions can be produced at the cathode by electrolysis of the organic whenever the triplet state crosses the PE surface of S. Interesting examples are found in substituted anthracenes. to T and r. state is yield is nearly unity. When this electron recombines with the dye cation. and S. Now slightly above the zero-point energy of S . The T. lifetime of S. emission is a rule rather than exception. transfer to T.icli:itiue trm$ition\. (4-7 kcal). A = 1 klr. Under high intensity irradiation and in rigid probable because of unfa\ourable Franck-Condon factor. mot ions. For 9. kl being the rate constant for crossing over from zero-vibrational level of S. molecules are generated. can return t o the ground state by a number of fluorescence quantum yields increase steeply with decrease of temperaturet ~hotophysicalpathways. In general. At the same time the quantum yield of product~on of trip'et decreases with decrease of temperature. is less recombination mechanism. which is equivalent to 1-2 quanta of vibrational energy of luminescence initiated by chemical reaction and not by irradiation. a barrier to inter- in the next higher energy state. is considerably aboke S. whilc sid3-subjtituteci derivatives have l o w yield and small temperature 111 mdiarionlcsi or nonr.. excited and ground state. state at a position compound. (C) Rcco~r~binatiorl I~rmirrescei~ce. Tj -Tx. clscironic cncrpy is dis~ipsleJ 35 dependence. The dependence is of the kame form as already mentioned.e. singlet. At low temperatures and rigid glassy medium. state.and 9. But the energy of activation obtained in this case is of the order 5. Experimentally. media. with very low efficiency in rigid level. When the two are brought together. 10-substituted anthracenes. state with observed in dye solutions in low temperature glasses is by cation-electron respect to S.so generated will diffuse into the solution. On the generated and a photon is emitted as fluorescence. the two may barrier. if T. But if T. a n atom or a molecule. The inte1:sity of P-type delayed fluorescence s h o ~ ~ ldecrease d with Anthracene has a triplet state T. -0PHYSICAL PROCESSES IN ELECTKONICALLY EXCITED MOLECULES 161 160 FUNDAMENTALS OF PHOTOCHEMISTRY the decay constant of the latter may be used for the determination of the + where A and B are constants. is nearly at the same energy as S. some of which are radiative and others nonradiative. i. an S. This energy barrier to if the polarity of the electrodes is reversed A+ will be generated.10 THE EFFECT OF TEMPERATURE O N EMISSION of temperature coefficient for the viscous flow. The variarion is of the form "all v i b r ~ t i o ~ qu. viscosity and should be observed.. the natural radiative lifetimes of fluorescence and phospho. After an initial act of photon absorption. a dye molecule can eject an electron which is trapped in suitable quence. fluorescence quantum yield should be less than unity excited state which eventually can relax by emission of radiation. states are affected to different extents by substitution. if at all. other hand.Still another kind of delayed emission The temperature sensitivity arises due to disposition of T. state. is sufficiently below S. If the transition ic within the states of the same multiplicity such as singlet-singlet. so that the density of state is high A similar phenomenon of cation-anion recombination may generate an at the crossing point. The lifetimes and quatltum yields of fluorescence of substituted anthracenes show Summary different dependencies on temperature. No dependence on temperature is expected. This transition is of the form r a E l k T where AE is the height of the energy will also diffuse into solution. The position of the substituent is more important than its nature. constants. if not consurncd by photochemical reaction. which is about 650 cm-' below ths S.lnta ~ : ~ l in which rhc environlnent acts as the lieat sink. The as triplet transfer is fecllitated. This is simple vibrational modes. If T. Again no temperature dependence is process can be explained as follows: a radical anion carries the extra electron observed. But the emission intensities The temperature sensitivity of phosphorescence mainly arises from fast may vary due to other temperature dependent and competitive rate impurity quenching processes. AE is found to be in the range of 17-24 kJ mol-1 combine to generate A* and A and cause cherniluminescence. fluorescence is the easiest way for deactivation and fluorescence sites.illshow temperature deficiency in the ground state. if it is . dependence. it is termed internal conversion (IC). The anion A. log . The role of viscosity in PROCESSES such cases is apparently to decrease energy degrading vibrational-rotational In general. the radiative t r i ~ l e tstate lifetimes.

F einstein s-1 where 4T is quantum yield of triplet formation. the fluorescence spectrum may appear as a mirror where k& is therate constant for intersystem crossing. pathways for triplet state.r*) w+3(7. The fluorescence yield 4. k ~ 21 c 1013 - 1012s-l. Therefore. enhance constant kNR is given by the theory of Robinson and Frosch as.A\+ 3 ( ~ 2 . fluorescence should be a linear function of state to the other at the steps: (i) horizontal transition from one energy concentration and hence a sensitive analytical tool. S. 3 .*) .+So) are less eficient due to larger enerev gno AE function of )i or This is known as fluorescence excitarion spectrum and. ) Or l ( t ~w. radiative transition probabilities. einstein s-1 The rate constant kl for fluorescence emission is related to natural radiative lifetime T.(S1+So) .. sing rates. The ~ b a l x the emission spectrum is independent of the exciting wavelength. Fluorescence appears mostly in molecules with conjugated system of double bonds and rigid structure. r*) w-+ ? ( I / . as a k l c (S. is defined as intensity of emission -. These compounds emit phosphorescence radiation a t low temperatures which are in near resonance with the zero-point energy of the transferring state in rigid glassy medium. That for intersystem (i) If fluorescence intensity is measured as a function of wavelength or wave- number of excitation radiation of constant incident intensity I. The interaction energy is computed from the exchange integral l n the presence of other competitive deactivating prmesss. 2:' d ~ .. a*) related to observed lifetime T. LI w-f u and S l ~ + T l The phosphorescence lifetime :T in the absence of nonradiative transitions is Transitions l ( n . is Fluorescence always occurs from the lowest singlet state even if the initial excitation is to higher energy state (Kasha's rule).=_. triplet state. a*). from the lowest triplet state TI gives rise to phosphorescence emission. isoenergetic point. or Tk.. Hence. For n-tn* transition. P2 is the interaction energy which couples the Born-Oppenheimer satets and is 8. . in general. Allowed transitions are: '~=lntensity of absorption (SlcSo) g *+g. I0 . The theory of radiationless transition considers the transition to occur in two (li) For low absorption intensities. and under - crossing XIsc is reduced by a factor of 10" 104. Sl w+ TI. due to violation of spin tun. it is termed can be made : intersystem crossing (ISC). Heavy atom substituents like halogens. l ( w . Azulene and some of its derivatives are exceptions to this rule. 5.a)* state as the lowest excited state are fluorescent. ' f the same configuration space. %+So) and kZsc (TI . fixed experimental conditions. in between the two combining states.is the Franck-Condon overlap integral. r: is inversely related t o k. $faintensity of absorption(SltSo) -I. Ea.303 ecl. but those with l(n. The rate constants for internal conversion are of !Ile order of vibrational frequencies. and image of the absorption spectrum for large polyatornic mobules.162 FUNDAMENTALS OF PHOTOCHEMISF!~~ p m ~ ~ ~ H ~ S I PROCESSES C A L IN ELECTRONICALLY EXCITED MOLECULES 163 In the case of small fractional absorption. F=+". . Furtheirnore. the variation of fluorescence intensity will servation rule. nonfluorescent due to longer radiative lifetimes and enhanced intersystem cros- where pE is the density of vibronic energy levels of the lower energy state El.. the rate constant for The radiative transition between S1+So leads to fluorescence emission and that phosphorescence emission in the absence of all nonradiative deactivation from T1+So t o phosphorescence emission.2. The radiative transitions can occur (a) from the lowest excited singlet Sl to assuming that all those molecules which d o not fluoresce are transferred to the the ground state So and (b) from the lowest triplet T1 to ground singlet So.. n singlet-triplet energy gap A % is governed by the electron-electron repulsion term. Because of vibrational relaxation of initially excited vibronic state.. and 12. actual lifetime is give' K which depends on the ovrrlap between the single electron orbitals. Organic molecules with l(r. intersystem crossing and hence reduce S. the molar extinction coefficient of the emitter. The rate 7. A ESTis small because 'i of the small overlap between n and w* orbitals.+So. The selection rules for radiationless transitions are just the opposite of those for Intensity of phosphorescence emission (TI-+So) radiative transitions. The actual lifetime r. . for the two combining states and (ii) vibrational relaxation of the lower energy state. The quantum yield of phosphorescence emission $. 4 and )*. is expressed as 4. The radiative transition TI-So. general ordering of . 1 kf v+x* transition.+So. The transitions from the lowest excited state to the ground simulate variation of e. . as are more prob~blzthan i. A EST is large because n and n* orbitals occupy more o r ?fEkf + ki and Of =a=~T~A. N =x Tf '' b i t i o---. 6 . The step (i) is the rate determining step.. . as 1 1 is Wnerally much greater than!T because of the forbidden character of Tl+Sa . should be identical with absorption spectrum. * ) ~33(/1. w * ) state as the lowest excited state are. . n*). general. two observations between the states of different multiplicities St m-t Tk. proportional to A E. T. - h.

r . (iii) Electrochemiluminescence is observed when radical-electron recombination reactions occur in rigidmatrixor radicals A+ and A. Bimolecular Processes (ii) p-type delayed fluorescence is cau3r. FUNDAMENTALS OF PHOTOCHEMISTRY energy states in a n organic molecule with heteroatom is l(n. Collision numbers or frequencies ZAB or ZAA are defined tor unit con- centrations of [A] and [B] and for molecules of common diameters and Weights are in the range 10' . 10. x * ) > 3(n. the collisions are defined by gas kinetic theory based on a hard sphere model. For a molecule in the excited state. Rate constants for photophysical unimolecular radiative processes can be obtained from spectral data and kISc and kTsc computed therefrom. n*) > l(n. 6. Photophysical Kinetics of molecules transferred to the triplet state nonradiatively are promoted with the help of thermal energy. to the singlet state from where they decay radiatively. M A and M B being the molecular weights of A and B.u ~y triplet-triplet annihilation process which generates an excited singlet and a ground state molecule. 1 2 . when two spheres are in contact. The 'closeness' of approach is a variable term and depends on the nature of interaction between the two colliding partners. 'I'he (i) E-type delayed fluorescence is observed in dyes which have small AEsT. [A][ B ] and 2 + where p. The rate constants for radiationless processes are important parameters in photochemistry because the lowest singlet and triplet states are seats of photochen~icalreactions. This is a biphotonic process and emission intensity is proportional to the square of the incident intensity.generated in electrolysis of organic compounds combine to form A* and A. there are few other delayed emission processes which have same spectral characteristics as prompt fluorescence. which in normal terminology is called a collision. Besides long lived phosphorescence emission. respectively. direct contact between two inter- acting partners may not be necessary and effective cross-section for optfcd . The excited singlet then decays radiatively. [?T2 r:. respectively. Temperature has no effect on intrinsic transition probabilirles or fluorescence or phosphorescence but emission characteristics may be affected by other temperature dependent nonradiative competitive Processes. 11. n*) > 3(77. which has spectral characteristics different from fluorescence. the reduced mass = M A M B / ( M A M B ) . = + ~ ( r ~ r ~=) the sum of the radii of molecules A and B in centimetres and defines the collision Qoss-section ok (= ~ r i B )in cm2.1 KINETIC COLLISIONS AND OPTICAL COLLISIONS The primary condition for a bimolecular process is close approach of two molecules.10lo 1 mol-I s-I at ordinary temperature. The number of collision per second between unlike molecules A and B and between molecules of the same kind are. n*). For ground state mole- cules.

HgCO (3Z) 4Hg CO(lZ) interr. (i) Electronic energy transfer to the added gas molecules resulting in Mercury photosensitized reactions are an important class of gas phase excitation of the latter ( E . The eflective crosssection o = ( I I R ~ for ) optical collisions is pro. a correlation W@ Pmbable mechanism. This approach is normally used for atomic gases and HgCO (lZ) -+ Hg (6l So) + CO (X1 C) v' < 9 dissociation vapours which will be discussed first because it has provided a wealth of A similar mechanism is now suggested for quenching by NO. (iv) Quenching due to abstraction of H atom.1). In the classical work by Zeemansky. These energy transfer reactions have a large crossaection for quenching and will be discussed in detail at a later stage.) +CO (X1 Z) -+ HgCO (3C) or (3n) complex formation interact with another rnolecule to bring about a physical or chemical change. portional to the square of distance RAP over which the excited molecule Gas Hz0 DzO NH3 NO COz N2 Hz ~ u more t recent work using flash excitation has shown that Hg (63P0) may not be the final state in all cases.2 BIMOLECULAR COLLISIONS IN GASES AND VAPOURS AND known to be good quenchers of excited states. itself being transferred to high vibrational level (v = 9 ) through the intermediary of mercury-carbonyl Figure 6. strong interaction between the excited atom and the quencher appears essential for quenching to occur. which probably proceeds as characteristic emission from the added gas with concomitant quenching of follows : mercury resonance lines. It is a spin forbidden transition and hence has long lifetime ( T ~ 110 ns). N2 were found to be very efficient ~uencher' some of these mechanisms may be explained by the potential energy (Table 6. Examples are: mixtures of Hg + TI and + Hg Na. molecules like NO. pfl~~~PHYSICA KINETICS L OF BIMOLECULAR PROCESSES 167 TABLE 6 . (iii) Quenching by inert gases like argon and xenon. Both saturated and unsaturated organic compounds have been found to (ii) Energy transfer in the vibrational rrloder of the quencher ( E a v be good quencherr. These gases ame 6. Such a process results The basic mechanisms may be identified as: in the formation of free radicals and consequent chemical reactions. Thus a information about the mode of excited state interactions.ystem crossing It is different for different types of reactions and for different types of molecules. and the vibrational energy u e l ~ .. Condon principle. ~ i m p l t of the quencher. . In many cases. collision. CO.).) . Hg(63P. This state is Hg (63P. Such transfer may result in the Wtions. some form of association involving established between the quenching cross-section and the close matching of *omtion JO rr-electrons into vacant atomic orbital of mercury seems energy difference. It is true for N. In others. Xenon is observed to quench by forming a complex which dissociates on emission of radiation. 1 collisions may be much larger than those for kinetic collisions (Figure ~uenchingcrosssection of various gases for mercury resonance radiation 6. Hg (63P. There is also the possibility of energy transfer to the triplet spacing Av of v = 0 -r v = 1 transition in the quencher.1).1 Schematic representation of (a) kinetic collision and (b)' optical complex formation.Hg (63P0). The simplest s quenching by Hz. H atom abstraction may be a very transfer).r E transfer). Conversion of a large amount of electronic energy into populated through 6T1 t 61S0 transitions by mercury atoms and emits translational energy is not a very efficient process as formulated in Franck- - strong radiation at 253.7 nm. It is expected that in such THE MECHANISM OF FLUORESCENCE QUENCHING cases electronic excitation energy can only be dissipated as translational The quenching of resonance radiation of mercury from excited 6% energy (E 4T transfer) because energy levels are much above state by large number of added gases has been studied. The mechanism of quenching is not the same for all the added gases. but CO deactivates the excited mercury to ground state Hg (6l So).

(c) and (d) types. a statement of the Franck-Condon principle. 2 Disposition of potential energy surfaces for the interaction between fluorescent in presence of deactivating gases.Ion- quantitative. This is called an encounter. Many collisions are necessary to deactivate a molecule with high No quenching E --E +T transfer vibrational energy because only one or two vibrational quanta can be trans- ferred at a time ( A v = & 1 for a harmonic oscillator. initially far apart. Eventually. This is. now which may have following dispositions. again. The reason is that any one of these modes may be in energy resonance with some vibra- tional energy level of the exsited molecule facilitating quenching by energy 'AB RA8 transfer. N lo9 . If a possibility of predissociation exists due to crossing of a repulsional PE surface with that of the first excited state a t a slightly higher vibrational level.:ty of the field effects makes them necessarily . Solute molecules. k. Once brought down to the zero vibrational level R a d ~ a ! ~ v quenching e of the first singlet state. between A* and B pushes the colliding partners a t this point of intersection* The liquid viscosity q becomes a controlling factor. The high kinetic energy of c o l l i ~ i @ ~ rate is limited by the rate of formation of new encounters through diffusion. The theory of such diffusion controlled reactions derived mechanism leads to dissociation of the complex. fiuorescence emission is facilitated. Collisions in gas phase need not always cause fluorescence quenching.:colIisional deactivation may prevent transfer of the excited molecule RAB to the repulsional state.168 FUNDAMENTALS OF PHOTOCHEMlSTRy ~HOTOPHYSICALKINETICS OF BIMOLECULAR PROCESSES 169 surfaces for interaction between an excited molecule A and a quencher B from the complex may be identifiable. Figure 6. b. After fruitful collision any excess collisions two molecules need to make before interacting is small compared energy is converted into translational energy of the partners. Such excited state complexes. whereby the electronic or vibrational transfer mech.) 6 . vibrational energy as vibrational energy and rotational energy as rotational energy. (c) The two *th the number they make in a solvent cage. By a balance of the two eventually separate as ground state molecules with large kinetic factors. Characteristic emission by Debye from Smoluchowski equation for rapid coagulation of colloids . 3 COLLISIONS IN SOLUTION (a) The two ground state molecules approach each other and no Gas collision theory cannot be applied to liquid solutions because of chemical reaction or complex formation occurs. in common liquids of low viscosity. associated energy changes the Franck-Rabinowitch 'cage7 effect. (d) A shallow minimum appears in the upper PE happens to lie in the same range as the gas mixtures. A radiative 1 mol-I s-I.101° surface suggestive of complex formation between A* and B. usually in- to each other. the bimolecular reaction repulsional curves cross at n point. with the minimum conversion to kinetic energy of translation. (b) The two curves tend t o volving 20-100 collisions. If the number of anism (E -+ E or E -t V) is possible. which in the gas phase is observed to bp Figure 6 . A polyatomic moIecule with many more vibrational modes is a much better quencher than a simple molecule. The interaction ketween one excited and the and hemmed in by solvent molecules make many repeated collisions with other normal molec~rleare also repulsional and PE surfaces run parallel each other before drifting away. the system attains thermal equilibrium when all the excess energy is dissipated to the surrounding. c. can only approach each other. Similar quenching studies for more complex systems have established that quenching is efficient when electronic energy is transferred as electronic energy. No quenching is visualized. are discussed later. excited and ground state molcules of a fluorescence A and a quencher B. come together by a relatively slow diffusion process. the interaction rate here energy of translation. d) : termed exciplexes. (See text for explanation of (a). > I for an unhar- monic oscillator).2 (a. Potential energy representations of molecular collisions go some way t o interpreting quench- ing but the cornnl~. Two solute molecules close together art repulsional all the tirne. P-naphthyl- amine is an instance in point. (b).

where I. is given by fluorescence by a bimolecular quenching step. In slich cases If another molecule Q is added to the solution which quenches the k . Since there is no competition with emission processes. [A*] [Q] )hen the concentration ef the fluorescer [A*] in presence of the quencher The oxygen quenching of aromatic hydrocarbons in viscous solutions is IS given as better approximated by this expression. i. Thus. and (ii) r . In some cases transient complex formation in the excited state may be involved (exciplex formation).e. and the probability factorp = I . These excited state radii (Figure 6. the rate constant k .170 FUNDAMENTALS OF PHOTOCHEMISTR~ TOPHYSICAL KINETICS OF BIMOLECULAR PROCESSES 171 is based on Fick's law of diffusion. where 6 If [A*]' and [A*] are fluores~erconcentrations in absence and in presence I'= . i. kf is the rate constant for fluorescence and Zkr. p is a probability factor per encounter. than A * + Q -+ A + Q Rate = k .sum of the interaction el. then This may cause immediate loss of electronic energy and is called static qlrenching.7). the respecti\ e quantum yields are en--1 E~T~AB . Basically. Ground state complex formation reduces fluore- Sence intensity by competing with the uncomplexed molecules for the If it is assumed that (i) a . if the diffusing molecules are much smaller than the solvent conversion k.ctron transft. For ionic solutions of charges ZA and ZB in a medium of dielectric constant E. the sum of rate reactions. In the limit this may just be juxtaposition of fluorescer and where k is the Boltzmann constant and r the kinetic radius of the diffusing . cules can move freely in contact with the solvent molecule. and intersystem crossing kIsc which originate from this molecules.2). KINETICS OF COLLISIONAL QUENCHING : STERN-VOLMER EQUATION A quenching process is defined as one which competes with the spon- Nlcous emission process and thereby shortens the lifetime of the emitting This involves the diffusion coefficients DA and DB for the two colliding molecule. Of the quencher. processes. Let r. the coefficient of sliding friction is zero.4. then on substitution in (6.l).e. molecule. the lifetime is not affected. the solute mole- energy state. the rate of formation of an excited molecule A* is equal to its rate of deactivation and the concentration [A*] remains constant : On further assumption that the interaction radius and the kinetic radius are equal. According to this expression. for bimolecular quenching reaction is given bv 6. a coulombic interaction term f is included in the denominator. = aB = a so ihat RAB= 2a. is the rate of absorption or the rate of formation of the activated controlled bimolecular reactions in solution set the upper limit for such molecule. The concentration of A* in the absence of any bimolecular quenching step is given as before (Section 5. a = r. we have the final form of the equation for efficient reaction. This is called the inner Jilter effect.pencher niolecules within the solvent cage at the moment of excitation. Under steady illumination. The calculated rate constants for diffusion.. = r~ = r absorption of the incident radiation. these quenching reactions are energy transfer or partners and the encounter radii RAB= a* + aB. constants for all the unimolecular deactivating steps such as internal However. bimolecular rate constant depends only on the viscosity and the temperature of the solvent. possibility of weak complex formation in the ground state is also *resent. u e have similar to the presence of other added absorbing molecules. The diffusion coefficients are given by the Stokes-Einstein equation may or may not emit their own characteristic emission which is likely to be different from that of the original molecule. ZAZRez and 8 =-. and r~ be the radii of the two diffusing partners. In solution.

/ - On the other hand. If r is measured independently then from the knowledge of Ksv. 0 D as given by the Stokes-Einstein equation is not applicable 1. K~~ is the reciprocal of half-quenching concentration or half-value concen- tration Ch. the rate constant k . 2 fluorescer A and the quencher Q. Either the diffusion Benzene 0. .17 Paraffin solvents) or the encounter radius RAB is much greater than the / gas-kinetic collision radius.. It assuming diffusion controlled quenching. For weak quenchers.o-range quenching . then The ratio of the two yields is C =2 = 1 + Ksv [Q].g.01 M and for 10% quenching. plot of + f O / + f vs [Q]. If /iqis assumed to be diffusion controlled. the lifetime T of This expression is known as the Stern-Volmcr equation and Ksv as Stcrn.. . the half-quenching concentration. [Q].. an efficier. for the bimolecular quenching step can be determined. The Stern-Volmer expresiion 1s ~ u ift r = s. cb--acter of an equilibrium constnnt. With rise i n ionic strength Values of k . .0 2. FUNDAMENTALS OF PHOTOCHEM~STR~ ~HOTOPHYSICAL KINETICS OF BIMOLECULAR PROCESSES 173 The quenching constant can also be calculated from the condition of 50% quenching. Ksv -. .001 M. then bromobenzene is a weak quencher for fluorescznce of aromatic hydrocar- bons.93 1. the quenching constant being nearly the same in hexane as in viscous paraffins.t quencher.. For ionic solutions.~ n colli- d Here. For The dependence of Ksv on solvent viscosity then disappears. implies a competition between the two decay pathways and has the [Q]. Unquenched molecule can be obtained from a knowledge of Ksv.54 3. decrease or remain unchanged concentration quenching.Ksv is the ratio of bin~olecular quenching constant to Strongly absorbing solution with fluorescence lifetime r? s and unimolecular decay constant and has the dimension of litrelmole. ~ A Z ~ ~ / T (6. ZA. Therefore. For example. 0. A z2 = z i Q . x 10-10 for anthracene fluorescence: A for O2 quenching. [Q]lo~l.102 . a modification of the / -.97 the quencher (e.31 Kerosene 2. ZQ are number and nature of charzes on the intermediate complex AQ. In such cases Bronsted theory quenching is diffusion controlled and is obtained directly from the expres- sion (6 4).103 1 mol-l and if r -- s. quenching of aromatic hydrocarbons by O1 in 0.( 2 . the reason for inefficiency may be that either a heat of activation or an entropy of activation is necessary. B for the quenching action may increase. Parameters in the Debye equation is indicated. where p is the ionic strength. C calculated from equation (6.. the TABLE 6 .. +z:) and ZAQ. if the rdte constatlt for the quenching step exceeds B C Solvent Viscosity in cP a t 25°C A that expected for a diffusion-controlled process. so that bimolecular quenching and is expressed as Ksv = p kq In systems where quenching is much smaller than that predicted by diffusion-controlled encounter frequencies.% is of the order of 0. an upper limit for k g may thus be obtained.13) (Table 6. all the encounters may not be fruilf~. respctively. The rate constant for bimolecular quenching collisions should be corrected to the limiting value koq according to which is of the same order as the encounter frequency. ionic strength is an important parameter.4).2).% = M.4 0. In the latter case a lon.0 0. IS the concentration of the quencher when the solution is half-quenched. 2 because the bulk viscosity is different from the rnicrovjscosity experienced Chloroform 0. For a Volmcr c o ~ ~ s t a n t . This explains the sensitivity of the linear in quencher concentration and Ksv is obtained as the slope of the long-lived phosphorescent state to traces of impurities.9 1.65 4. affecting the quenching constant.. . if the assumed mechanism of quenching is operative.: is the actual lifetime of the fluorescer molecule in absence of sional quenching efficiency p is less than unity. . If [Q]. on the sign of A z2. + log kg = log koq O .

-2.21) (ii) In the absence of static quenching a small positive deviation from the bher. In this expression. A sphere of transient quenching of volume I!. The expression becomes The fluorescence intensity F per unit volume is proportional to the more elaborate if the ground state complex also emits after excitation 0' ' ~ o n a llight absorption I# per unit volume per unit time. On this model. of quencher. leads to the non-steady state term in the quenching expression. given by F 1 = 1 +K"[Q] where K" = K' Ksv + and where E and e' are the molar extinction coefficients of A and AQ. F = +f I.174 FUNDAMENTALS OF PHOTOCHEMISTRY ~HOTOPBYSICAL KINETICS OF BIMOLECULAR PROCESSES 175 interaction such as electronic energy transfer is suggested.16) the simple relationship. the quantity on the left is the apparent quenching constant and varies linearly with [Q] with a slope given by the product of collisional (Ksv) and static (KO) quenching 6. The transient quenching accounts for the deviation from the Stern-Volmer relation in a manner similar to the static quenching but IC' is proportional t o . before a steady state is achieved.1 Deviations from Stern-Volmer Equation be defined as t l = 4x(pR)' 1/E (6. respectively at the wavelength of excitation. $tern-Volmer equation may be introduced by the transient component of simple quenching experiments can provide useful information regarding dynamic quenching.a) is effectively used for fluorescence emission and for small a. Therefore. and F are fluorescence intensities in absence and in presence is Unaffected.17) (i) Deviations from Stern-Volmer relationship may arise if static queccliing is present. the initial quenching studies of photochemical reactions./T does not hold. fluorescent complexes are formed in the excited state (exciplex formation and emission). may 6. (Ksv + KO)[QI + Ksv Ko[Ql2 assuming p = 1. Cl) = $f Io(1 .. p the probability of quenching and T guished by the following mode of action : the fluorescence lifetime and D = DA+DB.3 6 (6. the expression reduces to the Stern-Volmer type then the fraction a. If the complex is non- fluorescent. Hence.4. of incident light absorbed by the complex AQ is relation. where R is the encounter distance. they are powerful tools for mechanistic fluorescent molecule at the moment of excitation. only the fraction (1 . Fo/F = T.F F . so that Fo .\/E and lifetime changes with quenching although [F /* QI = (&v + KO)+ Ksv Ko[Q] (6. respectively.5 CONCENTRATION DEPENDENCE OF QUENCHING AND constants. For static quenching the constant is independent of D and the lifetime of the fluorescer molecule where F. If the quencher molecules are present near the the quenching mechanism. The EXCIMER FORMATION inte~ceptcorresponds to the sum of the two. and E = E'. Tke dynamic and static quenching may be distin. dynamic A* + Q + (A . df is the proportionality constant termed as the quantunr yield of .Q)*+[ + A Q f hv' A+Q+A hv t I Thv I where K' = vN = 4x N ( P R ) ~d E x static A+Q+(AQ) The total quenching consisting of transient and steady-state contributions If KO is the molar equilibrium constant for the formation of the complex is given by in the ground state For weak quenching. which is identical with the equilibrium constant.

which expresses the effect of geometry of the experimental setup on the measurements of fluorescence and absorption intensities must be considered. the intensity Figure 6.4). For dilute solutions.4 Variation in intensity of monomer and excimer emission spectra with concentration. But for many compounds. the term inside the brackct can be expanded. mental conditions are maintained fluorescence intensities and concentrations are linearly related according to the expression: where the symbols have their usual meanings. which is expected t o be independent of concentration.3 Plot of F vs C . If identical experi. simultaneously with the quenching of the normal fluores. 5 Potential energy surfaces for monomer and excimer emission. It follows the Stern-Volrner equation. [Q] represent- ing the concentration of the fluorescer itself. a factor G.3a. Furthermore. electronically excited dimeric ground state species. The decrease is due to the quenching of fluorescence by molecules of the same kind and is known as concentration quenching. The excimers dissociate when they return to the ground state by emission.176 FUNDAMENTALS OF PBOTOCHEM~STB~ fluorescence. A plot of F vs c should be as given in Figure 6. This shows that the ground state Figure 6. The fluorescence intensity should remain constant for any further increase in concentration... The quantum yield #f. On the other hand. negative results for the presence of ground state dirners. (4 +f VS c. . vg monomer and excimer emission frequency. This pheno menon was first observed in pyrene solution by Forster and was explained as due to transitory comp1:x formation between the ground and the excited state molecules since the absorption spectrum was not modified by increase in concentration. (a) theoretical curve (b) with geometrical error. 1 Interplanar d~stance In some cases. v&. A: excimer. at high concentrations where all the incident light is completely abmrbed. These short. cryoscopic experiments gave Figure 6 . starts decreasing at the same concentration (Figure 6 . starts decreasing after reaching a critical concentration even if geometrical effects are avoided in the experimental setup (Figure 6 3b). the exponential term in the expression (6. 3 ~ ) . giving rise to a structure- Concenlrat~on less envelope for the emission spectrum. In an actual experiment. I cence a new structurelejs emission band appeals at about 6000cm-1 to the red side of the monomer fluorescence spectrum (Figure 6.21) becomfs negligible and F = +f I. lived excited state dimers are called ~ x c i t n e r s to differentiate them from AHA enthalpy of excimer formation.

. the charge resonance state. the interaction can develop into a stronger force and the interplanar distance further reduced to form stable photoditners through covalent bonds. If flat molecules form a part of properly oriented molecular - system. Excimer emission is often observed from planar molecules when the two component molecules are placed in parallel configuration The condl. The delayed excimer emission crystal lattice) (Figure 6. 9. the probability of excimer emission crystals. These observations are tabulated in the Table 6. which shows that the nature of the excited state is also important. . Excimer emission is known to occur in inert gases like He and X e Naphthacene No Yes lL. and (iii) that the interaction energy between an excited and a normal molecule is attractive such that the excited state enthalpy . The excimer binding energy is explicable as quantum mechanical interac- tion between the two possible configurations (A* A) + (AA*). 10-diphenylanthracene neither forms a photodimer nor emits excimer fluoreswnce due t o steric hindrance. 9-methylanthracene Yes Yes 'La Besides the prompt excimer emission. B. In Figure 6. For example.6 Excimer emission from crystalline planar aromatic hydrocarbons and The nature of the lowest energy excited state and types of crystal lattice. Emissian from the biopolymer deoxy- Naphthalene Yes No 'Lb ribonucleic acid (DNA) is due to excinler formation between the constituent Anthracene No Yes 'La bases.6). The mechanism is through triplet-triplet annihilation -. red-shifted structureless band due t o excimer may appear even Pyiene Yes No 'Lb at low concentrations (Types B. if the overlap is small as in anthracege a biphotonic process in contrast to the prompt excimer emission which is nwnophotonic. Process (Section 5. In 9-methylanthracene both photodimer formation and excimer emission is observed. anthracene forms a photodimer and no excimer emission is observed. The utility of xenon arc as a source of continuous high intensity 2-methylanthracene No Yes 'La radiation is due t o this e-mission.3. In some molecules. very similar to that observed in concentrated solutions~ Theexcimer is formed as an intermediate which may dissociate into a n The crystal lattice of pyrene consists of two overlapping molecules(Typ~81 excited singlet and a ground state singlet. known as an exciton state and (A+ A-) + (A.35 nm of each other. the structured monomer fluorescence is observed (Type A crystar Lowest energy Excimer Photodimer excited state lattice). (ii) that the concentration is high enough for interaction to occur within the excited lifetime.9B): a A + a A -+ A: -t A * + A A similar type of emission is observed from some crystalline hydro. 4 4 carbons.178 FUNDAMENTALS OF PHOTOCHEMISTK~ pHOTOPHYSICAL KINETICS OF BIMOLECULAR PROCESSES 179 PE surface must be repulsional.5. delayed excimer emission has 9. 3 Figure 6. the situation is qualita- tively illustrated by the potential energy diagrams. tions are that (i) the two planar molecules approach within a distance e 0. 10-diphenylanthracene No No 'La observed. pyrene crystals exhibit a broad structureless band in VEX ~ V D F the visible region.A+). TABLE 6 .AH* is greater than the thermal energy RT. The mixing between the two states creates the bound excimer state. For example. also.). whereas some of its derivatives with bulky substituents which hinder close approach give excimer fluorescence.

indeed is diffusion-limited. It is not essential that the eczimer shall b: ak. L. 1-diethyl-2. = F. TOPHYSICAL KINETICS OF BIMOLECULAR PROCESSES 181 180 FUNDAMENTALS OF PHOTOCHEMISTR~ Excimer formation has been assumed to be a necessary step in . &. But fluorescence spectra are unchanged although bwered in intensity.. The enciton interaction which provides part of the 1 where. d[AN]/dt= 0 and d[~:]/dt = 0. Auorzscent (step 7. The separzte pro~t. In contrast to flat aromatic hydrocarbons. and I$E as quantum efficiencies of +. Als > From the stationary state approximation. Step 5 is the excimer formation step. It may promote radiationless p r o c ~ within the molecule (step 8. vide Infra). This increase is due to increase & . binding energy for excirner formation is also responsible for absorption changes in the ground state stable dimers of dyes. We can further define. is the monomer l~fetime in dilute solution and is assumed to be involved in the photokinetic scheme are: excimer lifetime in infinitely dilute solution. vide infra). excirners are not observed in dilute solid solutions. Mixed excimers of the type (AB)* have been detected in liquid solutions. %. We get +h general. the expressions for the steady state concentration of [A*] and [A:] can be set up. centration quenckng. kef k e x ( A ] . respectively: that ke. Some cyanine dyes exhibit both < m n o m e rand dimer emission. . from concentrated solution with quenching centrations. .kf (ked + kc/ + keq) I* . The Stern-Volmer expression kex [A*] [A1 can be rewritten as C is the concentration of the monomer and we have. where exercise in a complex situatloa (Appendix 111).23) *W temperature (77K) phosphorescence..' T& final expression is in the form of the Stern-Volmer equation.[A] (6. 2-pyridocyanine iodide. a = ked + kef + keq = . Step 6.is the maximum fluorescence efficiency of the excimer at high con- emission from dilute solution. Because of the diffusion-controlled kinetics. may need an energy of activation. many dyes form ground atate dimers and sometimes larger complexes.g. and of excimer emission. The concentration 1 b = kf + k ~ + c k ~ s c+ kex [A] = g qunching constant can bo calculated from the Stern-Volmer equation for and kf + k ~ +c k ~ s c= - 1 'K *not very concentrated solutions of dyes in which fractional absorption by monomeric dye molecules is high. 1. We shall use the various involved in concentration quenching to set up a rate expressio~l as a . modification Ofthe absorption spectra takes place as a function of concentration and Beer's law is not obeyed.. In such cases. Rate For 50 % quenching klsc [A*] where Ch is the 'half-value concentration'. 1/Ch has been found to be viscosity dependent confirming . e. aggregation of dyer inhibits fluorescence emission but enhances h.. which is the reverse process involving the dissociation of the excimer into an excited and a ground state monomer.

(ii) Emission concentration depen. unless high concentrations can be built in intersystem crossing probability because of reduction in S. dissociation may 2. can be calculated according to the expression 6. ~ b s o r p t i o ~ spectra remain unchanged.84 1. Dimerization follows act of light Dimerization precedes act of light via an ion-pair complex. Dissociated in the ground state. The term excimer was coined by B.10 0. Ionization potential (b) Energy transfer mechanism. de by light emission.80 2. Absorption due to both perylene mononegative ion and (i) Broad structureless band shifted (i) Give sharp emission on the long ~ r y l e n e triplets is observed. Observed for planar aromatic hydro. attractive tendencies are usually greater. ence of the heavy atom effect and where the extent of charge sfer is large enough. Q ~ )+ IA +Q A + A -+ A * + A -t (AA*) + A A + (AA) -t (AA)* lvation is an important factor affecting such reactions. um considerations show that they facilitate change of electron spin. 6. @rease in the ionization potential of the amines (Table 6. t exciplex dissociation occurs with energy degradation via a triplet it from excited state of dimeric species.012 a.'5 Physical quenching by foreign added substances generally occur by two Quenching of acridine fluorescence in aqueous solution (0. The quenching efficiepcy increases with to about 6000 cm-1 to red of wave side of corresponding dimer the monomer fluorescence band. hv absorption..-T.2 1. solvents of high dielectric constant. Excited state dimers - Stable in the ground stateat room temper. however.5 1 07 wllide. Some distinctive properties of excimers and excited state dimers are tabula. 6. kcrease in solvent dielectric Constant and ionization potential of the 6. Observed for ionic forms of dyes in &nor and electron affinity of the acceptor. 8.4 0.45 0.97 2. ution of perylene in a polar solvent containing sufficient concentration creases with concentration. When two dissimilar molecules d 8. Excimer 1.24 2. exciplex lifetimes may be long enough for them to ature. absorption. because . carbons. es and some rare earth compounds. energy gap the use of very intense light.6. as when deoxygeoated 4. hv .6 QUENCHING BY ADDED SUBSTANCES TABLE 6.. as was first suggested by Weiss.03 M NaOH) at 25OC.38 0. No absorption observed. Intensity of dimer absorption band in. In some systems 3. *pic studies. depending on polar Interaction involves some degree of charge 7.29.10 Th~formationof excimers between ground and excited states of similar * IdcII~. bromides . Normally nonfluorescent. TABLE 6 . brought about by exciton splitting of singlet S.35 2.12). 4 'A* +Q -+ ('AQ)* -+ 3A +Q + lA +Q Distinctive properties of excimer and excited state dimers of such quencher molecules are xenon. If fluorescent.13 molecules has already been discussed. olecules with heavy atoms act as quenchers by an exciplex mechanism. molecules and added foreign molecules are called exciplexes. --- transfer. Stevens to differentiat. (ii) Usually independent of concentra- The solvent-shared ion-pair character of the exciplex increases with the dent. absorption.72 1. state (Section 6. Radiative transition strong. 'kognizably free solvated ions may be detected. gP 1A* +Q + (lAQ)* + (A*. Radiative transition weak.40 polarizability properties. ted in Table 6. PHYSICAL KINETICS OF BIMOLECULAR PROCESSES 183 e short life of the complexes. NH* 8.80 25. and the frequently formed complexes between excited fluoresceot 'Sum of the diffusion coefficients of fluorescence and quencher.1 Charge Transfer Mechanism: Exciplex Formation and Decay 7 ma 10 16 3. . tion. 'WNH. The free energy change AG involved in the actual electron transfer Process: encounter complex -t ion-pair.6. Quencher ID (ev) 102 cmz s-1 (I mol-1) 6. broad based mechanisms : * (a) Charge transfer mechanism. Emission characteristics. dimethylamine to give 80% quenching is subjected to flash spectro- 5. in contrast to ground state interactions.5). bromobenzene.4.00 21. More commonly.

H. the CT-fluoresc:nce disappears due to solvation of ion-pair to form solvent separated radical ions.:. 'E lectron transfer . AE.1 nonrelaxed precurser Exclplex C e ~ r l n n t ci o n DJ:r I 0 + A * hVE Figure 6. -+ (4 N (C.!c If definite stoichiometry is maintained in the exciplex formation.. .H. point (Figure 6.. Temperature dependence of fluorescence of this compound in methyIcyclohexane-isopentane (3: 1) solvent shows a definite isoemissive I D .C1.Br. The aniline group is schen~atically presented in Figure 6. "'.7 The dynamical processes of formation and decay of exciplex by electron donor-acceptor mechanism.. quenching may be said to involve H-atom transfer. ~HOTOPHYSICALKINETICS OF BIMOLECULAR PROCESSES 185 FUNDAMENTALS OF P H O T O C I ~ E M ~ S T R ~ polar solvents. The n-electron located on its N-atom interacts with encounter complex which relaxes to the exciplex state after readjust*. It is associated with the formation of a fluorescent charge transfer complex The fluorescence of a number of dyes is quenched by ions in the the excited state.t~.)$ A-) . formation may occur in competition to exciplex formation and also as a mode of relaxation of exciplex. > 'A* + 4 N (C. D ' A molecule.).:. An intermediate nonrei:!jed not necessarily coplanar with the phenanthrene moiety but is oriented electron transfer state (ID+ A-) is produced by electron transfe:. structureless emission spectrum lying at a longer wavelength.7. ii! tIie perpendicular to ii..C 2 0 r 2 SO. The geminate ion-pair (2D+. . isoemissive j)oirzt similar to i~osbesticpoint in absorption miy be observed.2 > NO.A I ' . distancc a in the solvent of dielectric constant E. If fast proton transfer follows electron tr~nst'eri. is the eleLti.ent the excited -electron system and an intramolecular erciplex with T-bone type structure is formed in rigid glassy medium where rotation is restric- of coordinates and solvent orientation.d decay of exciplexe. > > > > I. This correlates with the increasing ionization potential which shows that -t + A 4 N (CsH5)s b r + . Triplet formation and io~:-pair ted. an evcitatio~lenergy.'Ab& lead to radical ion-pair which decays via triplet state. 8 Temperature dependence o f fluorescence emission from 9-methoxy- solvents.8). An example of exciplex emission is the system anthracene or biphenyl and an easily oxidized amine such as NNf-diethylaniline. structured fluorescence reappears. In nonpolar Figure 6 .CNS. > F.': ci is the free energy change gained by bringing two radical ions to encoi:~. A S the solvent melts and movement is restored to the 1 .. fluorescence of the hydrocarbon is replaced by a broad and 10-phenanthrenecarboxanil. '( D'A. The absorption spectra are unchanged showing absefla order: of cornplexiag in the ground state.. ion-pair formation is very fast and the rate of fluorescence where E (D/D+) and E (A-/A) are. are reported for Pmethoxy-10-phenanthrenecarboxanil. In stronglx p l a r solvent. An interesting example of intra-molecular erciplex formation has been The dynamical processes of formation ai.Exciplex emission and isoernissive point. such as acetonitrile. respectively polarographic oxicia!ion quenching is diffusion controlled : potential of the donor and reduction potential of the acceptor.

S+)" -+ A S + Normally the quenching of the triplet states by the collisional process where S represents the solvent molecule. The quenching effects can be produced by splverlts in absence of any other added quenchers.6). 6 . Two types of perturbation mechanisms are O. -- dissolved oxygen. nitro- helps to conserve the total spin. . Hence the system changes The quenching efficiency by electron transfer appears t o decrease with with time and the process should be classed a photochemical reaction decrease in availability of electrons in the quencher for loose bonding distinct from the reverhible quenching reactions discussed aboke. It is not a single solvent molecule which receives the process. --t So. is forbidden by spin selection rules and is therefore inefficient. The high quenching efficiency of 30. The increase in the rates of intersystem crossing has . a close approach of the %' Processes in photochemistry.e. that is charge transfer from the fluorescer to the solvent it is paramagnetic.is due Ions of lanthanide series t o its paramagnetic property. . --+TI and T. earth ions. . They act by promoting intersystem crossing rates. Type of quencher One of the most important and persistent quenchers in solution is 1 mol-1 s-1 -. Stronger the interaction greater is the energy loss.) electronic energy transfer mechanism has become one of the most Because of the spin exchange requirement. 5 x 107 Metal ions of transition series chemical change is observed. The soliated ~lectronscan be A * + Q 4 A + Q identified by flash spectroscopic techniques. S. ethyl iodide. ?OF) . .)d-orbitals of solvated ions of transition metals >$orbitals of solvated operative here: (i) charge-transfer interaction and (ii) spitl-orbit interaction tare earth ions. In non.-. 1) is believed to occur via the triplet state during the encounter complex formation. Most of the energy degradation :jA*(: I) + 'Q(f4) -+ A(?$) + Q ( . ionic or radical products is often observed. 2 Quenching by Oxygen. CS2 (external heavy atom effect).63 Quenching of the Triplet Energy States of the type + A* S -t (A. Some solvents containing heavy atoms can induce enhancement of is spin allowed. electron but the complete solvent shell.NO. and fluorescer in spin state (SA > I).11 - -. Electronically excited organic molecules are often deactivated by one or two collisions with molecular oxygen. It allows photosensitira- P.101'' 02. - 6 . Irreversible conversion to rule. Enhancement ne classification follows the extent of overlap of the electron cloud of of forbidden So-+T. in terms of Wigner's spin conservation methane.-+ ('A*. C o t + and some rare charge transfer from the ion. the substrates are oxidized whereas in others no permanent Gr. absorption is observed il. TABLE 6 . It has wide applications as a fluorescer and the quencher is required. a r o m ~ t .186 FUNDAMENTALS OF PHOTOCHESIISTRY p H ~ r O P H Y S I C A L KINETICS OF BIMOLECULAR PROCESSES 187 the fluorespence quenching efficiency of these ions is related to the ease of been observed for paramagnetic ions such as Ni++. The paramagnetism of the perturbing molecule or ion phosphorescence at the expense of fluorescence. For in the complex. i.30. I . Nitic Oxidc and Paramagnetic Metal Ions Rate constant for quenching k.. of this process. e. which mixes the singlet and triplet characters: IA* + 302 -+ t 2 ~ +. triplets cases. However. The same is true of . Polar solvents may involve chemical interactions 6. ~hysicaland chemical changes in the acceptor molecule by the diffusion controlled. The overlap of p-orbital of pressure (Section 3. presence of high oxygen the Wencher with the fluorescer molecule. polar solvents dispersion force interactions are important. The reverse if the quencher is in a spin quantum state greater than zero (SQ > 0).g. then the collisional may also occur. . 6 Types of quenchers and the rate constants for quenching of triplet energy states -- -- -. In some - Gr.7). Such quenchers can be classified into three groups example for anthracene and carbon tetrachloride: (Table 6.NO. Hence oxygen quenching is *haaistic tool and in photochemical synthesis.+ 3A ''"Ebctmnie Energy Transfer Mechanisms 'A* + 30.

Hammond and his coworkers respectively.. A nucleic acids is termed photodynamic action. near or below the energy l-vel of the donor molecule. the electronic interaction energy Pel is given by It is called trivial because it does not require any energetic interaction between the donor and the acceptor. it causes radiation may be expressed as 1 imprisonment and can be important factor to be considered in fluorescence measurements. For irrternzolecular cases between CO. The Coulomb term induces subsequent absorption of the emitted photon by the acceptor: long range transfer whereas the exchange term is effective for short range D* -+ D + hv only. of electrons and nuclei of the donor with those of the acceptor plus the The nonradiative energy transfer must be differentiated from radiafii'e electron exchange interactions. It is merely renbsorption of fluore- pel = qi A qfh. Examplss of many such sensitized photoprocesses are observed iil photo. pe F is related have developed a very useful technique using the principles of energy to the overlap between absorption and emis5ion spectra. it may be recalled.. Thus. two different types of mechanisms are postulated for lhe nonradiative energy transfer phenomenon : 6. ~ / kp*+*. The transfer occurs before D* i:.2). D.6 Long Range Transfer by Coulombic Interactions Early observations on long range energy transfer were made by Franck . This can transfer the electronic energy to a suitable :ic. a=X~dr. For quenching by energy transfer mechanism. spe~iesremains unchanged. and H.5 Donor-Acceptor Interactions in Energy Transfer Processes The electronically excited D* (donor) is initially formed by direct light absorption. The process may be defined by the following two steps: (i) long range transfer by dipole-dipole coupling interactions. 4x2 -h FE P:~F (6. and hence. thus excited indirectly. XA* and X. . to radiate and hen^ . singlet or triplet. The A* molecule.O to produce carbohydrates as the stable yroducts. D + hv + D* light absorption by donor D*-+ A -+ D + A* energy transfer donor -+ accepto. Although called trivial. is similar to the one obtained for chemical reactions is photosynthesis by plants. the initial light af>. = Coulomb term + exchange term. They initiate reaction intersystem crossing (Section 5. p~ is the density of energy states. A*. I n general. (6. i r i ~ . X ~ d rl X . the initial and the final states on donor-acceptor distance. Such a transfer has the greatest probability if there is an approximate resonance between the donor and the acceptor energy levels. It may introduce error and distort emission spectrum qi =J. is given by the time-dependent perturbation theory.s known as nonrutliative tran:fer of e x : i r .30) plzotosensitizod reuctions.ceptor Radiationless excitation transfer occurs only when (D* A) initial + molecule A (acceptor) resulting in simultaneous quenching of 12* and + state is in or near resonance with ( D A*) final state and there is a electronic excitation of A to A*. The green ch!vrophyll intramolecular radiationless transfer rate for internal conversion and molecules of the leaves are the light absorbers. Pel is the total transfer between molecules for synthetic and mechanistic studies in organic interaction energy parameter and includes all the electrostatic interactions photochemistry. p m ~ o p H Y S I C A LKINETICS OF BIMOLECULAR PROCESSES 189 electro!lically excited donor molecule..+D*(2) 1 absorbing only that portion which overlaps its absorption spectrum.litable donor-acceptor interaction between them. are vibrational wave functions of D*.32) scence radiation in accordance with Beer's Law and shows r-2 dependence When properly antisymmetrized for two electrons only. One of the most important sensitized photo. the total interaction can be expressed transfer which involves the trivial process of emission by the donor and as a sum of 'Coulomb' and 'exchange' terms.= 1+D* (AS+D +A* di.)~ (6. This expression. Photosensitized oxidation of proteins and where XD.i t is specially troublesome in studies on concentration quenching. XD. can undcrg iarious photophysical and photochemical processes. energy. Such processes a. and 4C is A + hv -+ A* the perturbation operator.2.orbing where the last term F is the familrar Franck-Condon overlap ractor.{~D*(l) #A(2). The rate of transfer.:: (ailed kD*+ A 4x2 == - h FE V2 . If Ti and 'Pfare the wave functions for the initial and the final states.31) biology and photochemistry.. 66. F = x ( . the quencher must h3''e suitable energy levels. f X ~ . In these reactions.6. and (ii) short range transfer by exchange interactions. able .

which is usually of the order of 10-8s.10 Energy level ~A~eme for =sOnance energy transfer between a donor (D) and an acceptor (A). is much enhanced in presence of Hg-vapour.10).190 FUNDAMENTALS OF PHOTOCHEMISTRY ~HoTOPHYSICAL KINETICS OF BIMOLECULAR PROCESSES and Cario in a mixture of mercury and thallium vapour. Therefore. consisted of lines due to TI also. 9 A pair of coupled pendulums in resonance. which is known to induce transfer from Hg (@PI) to Hg (63Po). the time-dependent perturbation theory predicts that the proba- bility of energy transfer should be porportional to the interaction time t.12-+ Molecules have cha$acteristic vibrational energy levels also.6nm. the average donor-acceptor distance may be as large as lOOA or more. But if we consider that the period of orbital motion is 10-l%. Once in the 9 s state. i. in Hg atom requires 469.) transition is in resonance with Na(72Sl. A comparatively weak interaction between distant atoms or molecules may be sufficient for excitation transfer provided some kind of resonance condition is fulfilled. -t 32PlI. 5 x l e a moles-l.12 + 32Sl12)transition at 594. The transition 63P1 -+ 6lS. deficit (I 62 cm-l) from the surrounding. %lure 6. the density of states p~ in the initial The energy deficit 560 cm-I is made up from the relative energies of translation of the colliding partners. the larger will be the transfer of N2.9). .) at 475 Dm. 63P. The Na-line at 442 nm. t 32Sl12in Na atom.e. At the pressure prevailing inothe mixture. The excitational energy The concept of long range energy transfer in solution ivas first is easily transferred from Hg to Na atom making up the small energy by Perrin to explain concentration depolarization of fluorescence. The idea of resonance transfer between atoms can now be easily extended to mole- Resonant transttlons cular systems.) function of the extent of overlap between emission speztrum of donor and transition sensitizing the emission of Na (72SlI. A resonance condition is established as in a coupled system. the lifetime of s is comparatively long.) transition emitting at 442 nm is the most probable one which is they can provide a larger number of approximately resonant paths The then followed by Na(32P. When a trace of N2 gas is added. and hence 32PlI. Since some kind of coupling interactions are necessary. the probability of transfer is a the Hg(6sPo -+ 6lS. These observations can be rationalized with the help of energy level schemes for Hg and Na atoms. t 32S.4 kT mol-l of energy which is of Figure 6 .7 nm radiation. 475 nm line of Na is enhanced. absorption spectrum of acceptor. Theoretical considerations show that a critical interaction distance R = A/2x r 1000 A for the visible radiation may be defined for the energy transfer process in an ideally coupled pendulum. This is a large distance on the %atomicscale an* corresponds to a concentration of about 0 .I. Similar mercury sensitized emission of Na-vapour was noted in a mixture of Hg and Na-vapour. which is very weak normally. Na (92S. the emitted radiation. When a mixture of Hg-vapour (0. A rough analogy of such a coupled system can be drawn with two pendulums of similar frequencies. It may appear surprising that such long range transfer is possible at all during the short lifetime of the excited molecules. Fluorescence sensitization has been observed in gaseous molecular system like mixtures of aniline and indigo. hanging from a hori- zontal string. nearly equal energy to the transition 92S11.25 mm) was irradiated by 253. in addition to mercury emission lines. absorbed only by Hg atom thereby promoting it to Hg (63P1) energy level. is transferred to 63P0by E -+ V transfer mechanism. The vibration of one pendulum travels to the other via small disturbances of the string (Figure 6..2 nlm) and thallium vapour (0. In presence greater the number of such resonant paths. Now probability (Figure 6.

i>.? integral. : !:. excited states with a fiolt~!.-:-)!lisio. .xcitzd 3igher vibr:itional Icve!s of !hi: dolt.: . transfer . electric-dipole-magnetic dipole. = -i. The dipole-dipole term represents where ODA is the angle between the two vectors and O D and 0~ the the interaction betneen the transition dipole moments MD and MA of angles sustained by the donor and acceptor vectors. ~ Of the ei.. 2 ! ~ . pHO~OPHYSICP. The orientation factor r. P(:t . the last term is the Franck-Co~~dori factor a!rJ tfic sum is over all take rlcicc f r c n initially .. jbrs:i:jn.. the angular t i ? . 2 ) .rt. .4R PROCESSES 1. . n is refractive The Hamiltonian of the Coulomb term involves electrostatic potential index of the medium to correct for the field effect. for energy number of quanta emitted per unit wave number interval and normaliled transfer in solution. :i.at. actual radiative lifetime respectively of the donor.rz.' -::]. fA that of the acceptor in the absorption mode. .-r?nd:. :. is i h f*siir ~ .n~. + ~ .e-j.:r.~. for energy transfer is given by kD*.snd J is the spectral overlap integral..':?. .::.j ~ . respectively.~.- 9 r 2 ':'Dt:!.. ~ : ? j>. being a function of their spectral properties.r ..s 1. . become important at close The expression (6.::!I ..r. .. The electrostatic potential can be expanded into where the donors and acceptors are well separated (by at least 20A) and multipole terms of the type assumed to be immobile.: . For vibrationally relaxed excited state in which initial and final states where Ro is know11 i i s the critical transfer d i s t a r ? ~xnd ~ is characteristic f ~ i are weakly coupled lhrough a dipole-dipole interaction. 4 . the rate consta!!t a given donor-acceptor pair. . the factor depends on the orientation of molecules in the crystal (equation 3.:: .*.::: <.t?\:. ' . 3'he donor mojci .at-' 'xt.iiot)al ditdc:i:. .s ~ Here F D 6)is the spectral distribution of donor emission expressed in The final form of the expression for the rate constant kEr. . x is an orientation number..:!... Y2 j : . .. ~ ~ ~ :I. . The square of these transi. w fD is the oscillator strength of the donor in the enlissioa mode.: - . . . It applies strictly to those cases with those of acceptors.. .. Higher order terms such as electric dipole-electric lattice... :.%..~:.'- :j ! . . fD a 4 ~ 1 v2.t.-.3 cos OD cos €JA (6. In gases at low pressures.. . +D and T D are fluorescence effi~iencyand and E A (Y)is the molar extinction of acceptor as a function of wave.it h i + * .. . which is deter- mined by the spatial orientation of the two transition moment vectors.r .. with the donor and acceptor molecules.thql .:.38) In this expansion the dipole-dipole term is the most prominent if donor- acceptor distance R is not too small..i. . factor relating the geometry of the donor-acceptor dipoles. ~ T ~ Tj<: "p.-.. e2 V ".' *. ef30ior!t. ~ f:.:.. F. This expression wds energy operator for the interactiol~of all electrons and nuclei of donors first derived by Th.o..-+A (dipole-dipole) = 4x2 k.is an 'average' wave number f c ~ the transitions... where C' is a constant. Forster in 1946.:?'.-c :~.. .. In crystalline radiative transitions in the individuai donor and acceptor molecules Solids..tt. .37) can be written as approach and may be effective in crystals and highly ordered array of chromophores.::Af[~ri~~ztidz . ' . Cp.. N is Avogadro's number. KINETICS OF BIMOLECiJL. respectively.. IDthis expression.73).. :I. 8(8) It can be calculated from 3 knowledge of overlap integral J and quantum .... . . r!I. .. rrl . .d fji" .\'iii-ict .B.: :-. " ir.....93 and the final states (Section 5 .(dipole-dipole RS + dipole-quadrupole + dipole-octopole.) for a fixed geometry is given as r2 = cos OD* . quadrupole... . line joining the centre of gravity of the two vectors. . etc. distribution. r" 22/ for random tion dipoles is proportional to the oscillator strengths fD and f A for geometry as obtained in solutions and in gaseous systems. ~ .i:. i ~ :to : ..CT~ .. in ::iericiil!y cqxiibratei?. :. .~.03fi'r ~ t f .:% pssible fi!':! ~ I " X X Z ~ $ ' ICX i< s~3 ~cori. : . . . expressed in the units of litre mol-Is-' is to unity on a wavenumber scale: 0 where. .rp::z-..ik.. In such cases the spectral overlap is expressed by :.

. ....R0 can be identifird with the - $<E 2 $ ..:: 5 0 : and kETTD = 1 -. c j p o ~ dc!cctriz i ~ g dipo!. - E w $ 5 5 . 2 Zo ?r ?i Selection rules for the electronic energy transfer by dipole-dipole inter- 2 %? 5: actions are the same as those for ~ ~ : .2zZxN 0.[D*] r = J 7D . is related to R. (ii) there is significant spectral overlap.~CE g aoe 2 9 SU as23 2 g $4 k. The acceptor absorp- -2 52-* c . 5 2 which the donor solution is 50% quenclled is inversely related to Kqv - -* $ g " . The spin selection rule requires that the total multiplicity of the donor and tlze acceptor.5. molecules is less efficient than that between unlike molecules when acceptor . h 2 c0"e The average intermolecular separation depends on the concentration of .& o . E sf by the expression . The sreater the spectral overlap.: fian~itiuiib F.g where [Ao] is expressed in molecules per cm3. c'r Z :29": *$: is at a lower energy level (exothermic transfer). = k~ [D*] = .-$ a c the solution. An experimental value of Ro (in A) may be calculated from the half- quenching concentration data. I 1). is b'7 ~as ~ e ~ ~ 2 L-- m-c 3 ."I s. Z " in the isolated molecules.2 "$I. = MI\* - where M's denote the multiplicity of the sistes (Section 2. thcn R. * Q 0 2 5 A are predicted.J4 & can also be defined as the distance of separation between donor and 8 2. w .0. and 0 g '* (iii) the donor emission yields lie within 0. No transfer is expected if the acceptor level is higher than the donor level. transfer between like t. The critical concerztration of tlrc acccyfov A. ~HOTOPHYSICAL KINETICS OF BIMOLE. 0 . . This implies t h a t Mi!c MDand M.1).8 tion should bc on the red end of t i i t tla:ior erntssion The efEcizncy of transfer E.1 1. If (i) the acceptor transition 2."ULA:( I~KOCIISSES 195 yield +D of donor flmorescenc:.. . a0 0 6 5 1s strong (E." c o -f-.O .. Because of the Stokes shift for vibrationally relaxed systems (the rate ZST.O of transfer 4 the rate of vibrational relaxation). prior to and after tilc zrzt or transfer. valuts of 50-100 L " P 0 r.000). i 0 r r 0 E0 m0 (= kET T~). 3c . the more efficient 1s the energy transfer iF~gi:i: 6 . radius of a sphere with D in the centre and containing one molecule of A - - .. the concentration of the acceptor at : a GGr- :5 L. (6 ."-A [A].42) .:. [A].~2. 10.. must be preserved. -.43) c ti%* .- 0 1 only. Expressing the concentrations in moles per litre we have O C from (6. 0 F.3 acceptor at which the probability of transfer is equal to the probability of $5 2 decay of the donor : m < i 0-z 1 J z g u ker [D*] [A].

-. The rate of singlet-singlet energy transfer becomes diffusion limited and Forster's expression ceases to be valid. They are indcperldent of viscosity for 100-fold change. The criteria for long range energy transfer processes are that (i) the trawl -.ai..--.. intermolecular transfer may occur with reason- able rates. Scence and (iii) experimental c ~ l c u l a t i oof~ ~Ro and its colnparison with the theoretical value obtained from the FZjrater formulation. Triphenylamine Chlorophyll 54 N. perylene-chloroanthracene system.--.---. collisional transfer and excitatloll Jlligrd+ The r:~teconstant. confirming the predictions of (ii) the transfer efficiency should be independent of viscosity. : are greater than those for ditTusion-controlled among donor molecules weere avoided (Figure G 12). Forster's expression by carefully des~gned experiment$ I n wh~ch 'ii other mo&i of transfer such as tl~vldl processeb of reab\orpt~on. Long range triplet-sitzgl~ttronsfcr has been observed to occur effectively although it is a spin-forbidden process : D* (triplet) + A (singlet) -+ D (singlet) + A* (singlet) This is because the low efficiency of such a transfer is compensated by long lifetime. -- Donor . for transfer by a resonance mechanism (Table 6. . (ii) appearance of acceptor fluorc- Table 6 '. . If other modes of triplet deactivation are less competitive. x 10-11 Ro 6) i b * (ginglet) + . p. 1 2 Resonance energy transfer causing enhancement of fluorescence il. X .fcr is detected by the sensitiztios cf lcceptrrr flnorescence and the quench~ng of the donor fluorescence and i~~-~. - Singlet-singlet transfer by resonance mechanism . that is.) are Yery large as calculated from concentration should occur at distances much greater than the kinetic collision radli. If the absorptio~~ of the acceptor is sufficiently weak such as (n -+ x * ) trailsition in biacetyl. Acceptor k. critical transfer distances R. N-Dimethylamine 9-Methylan thracene 24 -. The slow rate of energy transfer is not incompatible with a large value of R.196 FUNDAMENTALS OF PHOTOCHEM~STRY ~HOTOPHYSICAL KINETICS OF BIMOLECULAR PROCESSES 197 The two spin-allowed processes are : TABLE 6 . Forster's theory. similarly forbidden.-.8)._ _ _ _ _ . Ro becomes nearly equal to the kinetic collision diameter. :<I! accep!oc iornplex formation. . 7 Singlet-singlet transfer : I)* (singlet) + A (singlet) -t D (singlet) A* (singlet) -. In such transfers . ? dependencc of quenching or sensitization. -- The :. TABLE 6 . Two most irnpc~~l reactions. 8 Critical energy transfer distance Ro from donor triplet to acceptor singlet (triplet-singlet transfer) Donor Acceptor Ro hi0131 cone of 8 Phenanthrene Fluorescein 35 Figure 6 .1 111s group Live unecjui.. exchange interactions may become operative...olves singlet states 11' Such transfers are detected by ti) reduction of the phosphorescence life- both the ~1-:lor and the acceptor (singlet-singlet transfer) as shown 1%' time of donor in presenee of accepior.p . Over such short distances.vocally estdbl~hhed thc premisl. .4 (rriplet) -t D (singlet) -t A** (triplet) 1 Chloroanthracene Pery lene 2 41 lC?iloroa~:tliracenc Rubrenc - 9 38 Hofilen 311. .

SD* = SA* and S. (ii) The magnitude of the exchange interaction is not related to rile oscillator strengths of the transitions in the donor and the acceptor.r?ci !he .l2. TI12 rate of transfer is given b) Figure 6. Thcre- fore. therefore. Benzophenone was found to possess the criteria for a suitable donor \!. By such con15inations {hi. no i i t 11: tilts <:spl. = SA. 2f!i't~ti\c a\er.lcccptqor.>r. betaeen the donor and the nccept.i?.6. The transfer occurs at diffusion-controlled rate.: a:. The characteri\tii. features of the exchange interaction energy are described beloiv: (i) The electrostatic interaction between the charge clouds will be large only when there is a spatial overlap of the donor and the acceptor wave functions. As a result.a radiation in respect to exchange of space and spin coordinates of any two electrons i n presence of suilable donor. i v ) is also norn7alizciI : \ Phosphorescence was observed in absence of benzophenone. But if the transitions are ailowed dipole-dipole interactions nlay take over.: of the acceptor iiaphth. or 'forb~ddennes~' of the trans1tio:i in the 'lcceptor. the tranil'er rates are independent of the 'iillowedness' overldp with thr: singlet-singlet a h s o r p t l ~ nspectrum of the acceptor. it can only be a short range phenomenon. F C J ~ forbidden transitions like singlet to triplet.could be excl!tdcd by using a suitable light filter t o cutoff radiaiion absorbed by the acceptor (Figure 6.t r i j ~ l i . .trdnsfer.in kinetic sense. occur by Coulomb interaction. B u t it is fully allowed by Wigner's rule since the total spin in the initial a n d the final states is conserved. Othei symbols have th~:ir Occurs with unit efficiency ( 4 1 sr ~ 1).tc N-" dependence on separation dlit The f o l l o ~ i n gtrii?lc t . f o r t11c initial ~ l n i ifiiiil Or sensitizer For this molecule. From the expression (6.~i.g: i . e .cep:or. The l or.:. I t is the same ~ i n dof interaction which causes sinpiet-triplet splitting. at a d~stanceR R. . exchange interactions will be predominant a t short distances. ~HOTOPHYSICAL KINETICS OF BIMOLECULAR PROCESSES 199 it is necessary that the phoiphoreccencc spectrum of the don01 S!C( unity. After .ter formulation predl.e. is the distance betnee11 electrons ( I ) and (2).7 Short Range Transfer by Exchange Interaction Intermolecu!ar energy transfer from the triplet of the donor t o the tripkt of the acceptor was first established by Terenin and Ermofaev in The exchange interaction is a quantum mechanical effect and arises 1952. An expression for transfer by exchange inreraction was derived by Benzophcnone Naphthalene Dexter for a vibrationally relaxed system. possibility of direct excitation of' the ac. thr dono1 :. the intersystem crossing ID* ht3 3D electronic st.13 Triplet-triplet energy transfer between naphthalene and benzo- phenone. N o transfer outside the boundaries of the molecule is expected by this mechanism. when the two actually collide . i .33) for total EID was higher than ET.!tiitl. iihere r . Under the experimental setup. 6. i. the rate of transfer is doubly forbidden by spin selection rules and cannot.13). Thcy de~nonstratci: >ensitizeci phosphcrrescence emission from because of the sqmmetry requirement of electronic wave furlctions with naphthaleiie i n rigid glassy mediun-i :!t 77K using 365 nl. I h e r e f o f e the r2:e of tran\r - expected to Inirease sharp11 \+hen distance 1s reduced and vice h t For example. 01.h i t ~ l i-. They choose donors whose triplet energy the donor a r acceptor complex.cs\iorl..hc-re !. According to the spin conservation rule.lice I p(:~j.tlene but singlet energy donor acceptor interactions ESD was less than Es. where S is the total A 64-times increase in transfer probability! spin wave functior?. F o r transfer by this mechanism the total spin hut not the total multiplicity need be conserved. i.

14.14 Three donor-acceptor energy level schemes for quenching by The quenching of donor phosphorescence is a function of the acceptor energy transfer.___--__. aron~cttic of donor phosphoresccnce is ~ndependentof the acceptor concentrati~~n hydrocarbons and olefi~ieshave convenient singlet-triplet ievcls to act as is expected from static quenching model.kT). the rat< 6. The critical separation distance remained unchanged when halogen substituted naphthalenes were used. The halo-substitution is expected to increase TIA M transition probability innaphthalenes. action' model was first suggested by Perrin for static quenching of fluorescence. + and respectively.t..r distance lie within 11 .e. On the other hand.N CA (moles/litre) in Figure 6. following scheme : . Figure 6.bcen observed in some aromatic hydrocarhone Tile two long-lived iripletq quenching IS given as A. concentration in rigid media and follows the expression: 2.8 Sensitized Delayed Emission constant for transfer by exchange mechanism cannot be calculated. probably due where +. [D*] [A]. In this range energy transfer may donor triplet in absence and in presence of the acceptor A at a concen. The transfer rate is diffusion-controlled even when ETD5 ETA. Benzophenone (D)+naphthalene (A). trarisfei is exothermic by 3-4 kcalj~cole~ 'hat of the rcspuairc trip1i. The Ilk' . CA is expressed in moles litre-'. show temperature dependence (AE .9). Since oscillator strengths f (naphthalenes. uherc the rate :)f has.6. Delayed ' ~ ~ e s c e n c ein nap1.200 FUNDAMENTALS OF PHOTOCHEMISTRY pH~~~PHYSICA KINETICS L OF BIMOLECULAR PROCESSES 201 followed the path: 'D -- direct excitation of benzophenone by 365 nm radiation the sensitization 3D 3A -+ lA hvp + The critical sepa~ationdistance calculated from the quenching data was found to be 13 A which is of the same order as the van der Waals separation. An interesting variation of energy transfer between two triplet molecules of the Bimolecular rate constants for triplet-triplet energy transfers can be Samecompound under conditions such that triplets can be generated in large n ~ r n ~ b e r s measured in fluid solutions only from quenching data. 1.15 A n i expected for donor-acceptor coll~aioncomplex. nhcrchy trlpleis are 'annihilated' giving rise to one biacetyl as donor fa11 into three groups depending on the position 0' '0l~cu1e in the e r c i ~ e Jlioglct state and the other i l l the gound strtc (Section 5. the values of critical tr~~~rs&.143: phenomenon is poisible in rnolecuies like naphthalene. both and is obtained from the quenching data after changing from per molecule singlet-singlet and triplet-triplet transfers can be arranged i n suitable to per mole unit: donor-acceptor systems so chosen as to provide conveniently located LOO0 In ($014) 3 . In practical application. the rate of transfer is - (T T) type energy transfer from a suitable donor is necessary. good sensitizers of triplet state N is Avogadro's number. Cournarin (D)+ benzophenone (A) (ii) When ETD. j Aromatic carbonyl compounds are. the quenching rate becomes at least a million times slower than the diffusion-controlled rate.the quenching rate drops suddenly. In rigid media. no increase in transfer efficiency is clear indication of the lack of dependence on the oscillator strength. energy levels. i.and a is a 'sphere of quenching action'. The values of quenching constants far EO'llde with c a c l ~viiicr in soiuiiun. For the generation of these triplets in high conccntra- transfer occurs on nearly every collision.nc because of \mall singlet-triplet splitting.thalene has been rensitired by phenanihrcnc.IIETA. i.R3 because higher triplet states get involved. It is defined as the sphere of radius R wherein an acceptor The effectiveness of an energy transfer quencher is determined mai~lly within the boundary is instantaneously sensitized but outside the boundary by the position of its lower triplet level and not by its molecular structure. For cnergy tran-fer by excli?-'$ good triplet que~ichersor acceptors. where Ve is the critical volume in crnvefined by the critical radius R. according t o the diffusion-controlled.e.. Three different quenching schemes are possible as shown Vc (in cm ) .lppcnr to hare the lowest singlet energy level about twice (i) When ETu>ETr.-. tration CA. mechanism. a i . has no effect on the donor emission. anlhracenc and each of u h i ~ hh. :f (iodonaphthalenes) is as 1 : 1000. probably a = $7. and 3. The 'sphere of quenching < (iii) When ETD Era by 3-4 kcal or more. Naphthalene (D)+ biacetyl (A). triplet energy ETD of donor relat~veto E r 4 of ac-eptor (Figure 6. are the phosphorescence yields of the excited to the possibility of back transfer.

Very fast intersystenl nonconjugated chromophores are found in the conforn~atirinalstudies of crossing in benzophenone-like molecules precludes the possibility of transfer biomolecules like nucleic acids and proteins. Tb"" and D Y + ~with electronic configuration (f throllgh ...2 by c.T type) Most interesting applications of intramoleclllar energy trarufer between after intersystem crossing in the carbonyl moiety. preclude direct conjugation between n:ipiitliyl and a:ltl:rj. In those systems \%.iFaorption spectrd o f ir~diircill t1 cl~ron~ophorei. x" and the excitation resides on thecarbonyl moiety. PTl and Nso. PSI. Chai~giiigthe il!s!:\l~i'e of scpara- tion by it~cre~ising the n ~ ~ i u b cofr CH..hereinternal rotation is compictely restricieil anti the absorbing and emitting chromophore angles can be established unequi- vocally.:ta.:l c-.~ ~ O U P ~ .3 cos O .(tl. x * ) +-+ T (*.rit. %*) *-+ T. Nicotinanide-adenine-dinucleotide (reduced) N A D H .. Although insulating C H . -+ S1(11. where N = naphth:.jssiori i h esclusivcly from :lnthr:icciic. trip!rt .t cxci!ed methoxy benzene and flourene chromuphere in norbornadiene-spirncyio- state is S ( 1 7 . Excitation el. The energies of the emitting levels are fairly loiv so that the rare earth ions can be very useful species as acceptors to detect ef6cient singlet-singlet ( S .!^ 111 the ground <tate Fd~reudln! 4 h e n ~ o'!biph.. Nsl. IIT. the Fiirster forn~ula'cionwith x2 = cos2 OD4 -. betvieen S (n. If tllc naphthyl group is sir~~ilarlyaftnchcii :. Such quenching processes alene is excited by light absorption. for type (iii) system coumurin and benz.r. I hnr. 9 lntrarnolecsllar Energy Transfer All kinds of internal conversion and intersystem crossings are .ii:itr~stic of bipliciiyl. (I) the '~biorjitii. the e.: estnblibht.enzophenone both (S -.10 Energy Transfer in Rare Earth Chelates In con~poundslike: Rare earth ions.6. 4 . interact it.:escence emtsstorl i. + hv. S~rnri. -1 synthesizi~~g rigid molec. n*) of biphenyl.niati~~n. . becn obscrved to occur even a hen thc chromophores are sep.! -. scheme for two illdividual moieties is as given in Figure 6 . x*) -+ S.. p- scheme (i) as given in Section 6. The 1owes.f 9.! moieteis.S) type energy transfer occurs when only naphthe triplet states in solution by energy transfer.2 The of the orientiition term K" !?as he!:. S" 6.~~1s vei. The sequence of tional depolarization of emission from intrinsic fluorescent groups on events is. knowIedge which has helped to enrich the subject of photobiology. The excitation energy is transferred by exchange mechanism (T .ne for riaphthyl ketones (11) TIleie compounds present ellerg.ti:il sp.15). The Pso. Oligomers of poly-l-proline vvith a-naphthyl group as energy dotlor and dansyl group as encrgy :lceeplor. first excite. x*) of C = 0 to T(x. ( n .. The m!iz of cnrrgy transfer can be traced as follo\vs: 6 . l-anthryl-l'-naphthyi alkane>. n*) of biphenyl is lower than the T. Anthrone and naphthalene cbromphore i n T(n.nyl . 111. I Snl'*-.hocpll. externally attached fluorescent probes. ~. hsve resulted in a vast store of So + Rv.ophenone..ii ..:spectively the ground state.lene anti B = ben~nphenori~.:ccr r. tl:c figure are.7 (Figure 6. wh ch intitcutL there is little. especially E u + ~ . if an). I.S) and (T . . 14).o 'r.T) types of transfers are possible..6. NT1 are r. The conlpounds gitea ii. 11.emit charac~eristicline spectra from their 4f energy states. GO? Oh agrees with experiment (Figure 6.S ~ I + Gd+3. .-groups docs nor ::!kc[ the transrcr ejjcietlcy. molecular energy transfer within a chronlophoric group. But the propane frame. V and VI. The experiments on rota.4 I I ~ ~ L !~lte ~ I benrophcno. x*) state of benzophcrlone spiro-compounds.:c molecules of phenanthrt:!:t and naphthalene. rt transfer uithin a molecule from one chromophoric group to anathi) . 6 .iraf lnsulnt~nggroups The ab~osptlot spectra of thece cornpounds are I !lit: .ules with suititblc spa.

(ii) L. w+ 1T.+ gi~~iid Energy transfer from singlet or triplet states of suitable organic molecules If the liga~tdtriplet lies more than 2-3 kcal below the enlitting level of the a n cause excitation of the central ntktal ion in a coordination compound. Few other schemes are also more than that of (NCS) for the sensitized reaction. 6. + M* -t M..)6 (NCS)2+ ion. (i) Ls. khereas it is visualized depending on the relative energy levels of ligand and the metal Ody 66 times on direct excitation of Cr(II1). transfer may occur from the singlet state of the ligand to the the ligand lies a b ~ v ethe emitting energy level of the ion. If suitable coupling interaction appears as the line emission of the central metal ions. wn.) is hundred characteristic of the ligand is observed. 11 Energy Transfer Processes Involving Coordrnar~onCompounds ligand ligantl metal metal sing!et ?rip!et AL. The rate of energy transfer probable path of energy transfer within the chelate is: k~~ 1010 .11~ molecular energy transfer. 1 Rare earth ion CGNH OMe IV PI Figure 6. such as the diketone-l. Figure 6.16. 4-hv follow the Stern-VoImer equation.Lcd cv-. Energy level scheme incorporating probable pathways for energy When these rare earth ions are complexed with suitable organic ligan~is~ transfer within the chel-ite i b given in Figure 6. 3-propanedione.) w+ TI ~3M* 4:< TI) 4 M. Photosensitization of Cr(I1I) complexes by biacetyl leads to aquation ions. energy is nGt transferred and broad molecular phosphorescence reaction of Cr(NH. energy absorbed by the ligar d transfer occurs by exchange mechanism. such as: . (i) Ls. The aquation of (NH. if the triplet state of exists.+ M: ( > T.lOl2 s-I IS predicted.16 Energy transfer pathway in rare earth chelates. FUNDAMENTALS OF P H O T O C W M I S ~ ~ flopHYSICAL RINI?TICS OF BlMOLECULAR PROCESSES I I Chelal~ngagent. *-+ L T (>~ TI) *-+M* -+ Mo 4. from which the lifetime of triplet + (iii) Ls. In these chelates. The nlosr higher energy state of the metal ion. *--+ M* + M O h~ molecules TD can ue caiculated.15 Structure of some flexible and rigid molecules which show intra. This shows that energy ions.6.

~is observed with high efficiency. The interaction is highly geometry dependent Present in trace amount is observed. Using time are oxazole and oxadiazole derivatives. The wave function for these two descriptions aredegenerate. At very close separation of the dorlor and aci<.. This molecule then becomes the centre of emission with high varies between 2000 cm-l for a strong coupling case and 10 cm-l for a efficiency. they are plastics or other polymeric materials. There is no rnay be considered t o be excited. The scintillator diphenyloxazole dependent perturbation equation. Iu solution the process can be kinetically treated in terins of contianing very small concentration of naphthacene -.: states are well separated (Section 8. impurity. the lowest doublet and quartet c i it. has been established that photoaquation of cyanide ion occurs froi-. Such solutes are called liquid scintillators and are widely used weak coupling case. . Pt ji[H). A set P-terphenyl is excited by x-rays or y-rays. Similar ser~sitized aquatiorn and redox reactions are observeil for Co (EIH). a set of from guest molecules suggests that the excitation energy explores about degenerate energy levels is obtained in which any one of the N molecules 10s lattice sites during the lifetime of the excited state.12 Fast iMmltisitctp Migrstiaol of Excitation Energy Figure 6. molecular crystals or linear polymers.. ~noleculeswe have seen ?hat Forster type pure dipole-dipole resoi1. can be described as AA* and A8A. The important scintillator solutes important for energy migration or exciton delocalization. In the !imiting case of a crystal or a :cry the fastest rate predicted by any mechanism.ri a greater than that calculated for diffusion-controlled rate. created in either molecule. destroys the degeneracy.6.6) By the use of suitable sensit!z:. lo-' ppm as trace ral?dom walk of the excitation. When excited in anthracene absorption band. The host-sensitized emission as ~nolecularaggregates. Monomer d~mer Monomer d ~ p r 6. Even when the splitting is concentrated solution. emission from the solute of two energy levels results. the excited state and many other biological systems.~nce transfer can beconle very fast. is given as is commonly called PPO. (b) Liquid scintillators. The transfer rates are proportional t o K-s.i.. for detection of ionizing radiations. .ir:~~ molecules.~citonirar~sfcr. Because of the close proximity of like molecules excitation where R is the distance between the centres of the two molecules and G energy migrates from solvent to solvent until it is captured by a solute defines the geometry of stacking (Figure 6. A well known particular time and orre speaks of' an excitor? process or ~ic/oii~/i.. The interaction between the transition transfer if these crystals are dissolved in fluid or rigid solutions.. and Ru (11) complexes.. time period for transfer T.17). For example.17 Exciton splitting and geometry of ordered array of planar ( a ) I?. emission from In systems where the molecules are stacked in defined geometry such haphthacer. In-phzse and out-of-phase interaction of transi. In hexacyanochromate ( H I ) ion.iblet crossing is not always fast. whereds BEg state is photochemically inactl-4. In such systems excitation energy and the energy difference AE between the two exciton levels is given as supplied by the ionising radiation preferentially interacts with the solvent and finally resides in the low lying excited singlet state of the solvent molecule. toluene and xylene.ahlch favours photoaquation of ammonia. Sometimes they ate embedded in Although all the exciton levels are not equally allowed. Such dipoles of these zeroth order states causes the splitting of the energy exciton transfer modes are said t o work in phbtosynthetic units in plants levels (Davydov splitting). the nature of solvcnt Ttt = KEh r 1014 S-I (for AE r 1500 cm-') (6. Good scintillatiori solvents are generally snsaturated molecules such as benzene. The interaction energy molecule.[ is possible to excite the two states separately. for a dimer AA. excited quartet state Tz. the trarrsfer rate is so high that the excitatioi: :an about 10 cm-I the rate of exciton migration is fairly high and much no longer be regarded as associated with any particular molecule . For liquid scintillators. If a very dilute solution of anthracene or tion dipole M.~d example of such fast exciton migration is a mixed crystal of anthracene cxcitatiot:. #HYSICAL KINETICS OF BIMOLFCULAR PROCESSES 207 transfer occurs from biacetyl triplet to the quartet state of Cr(llI) . By such techniques.49) is also important. the seat of phosphorescence emission The intersystem quartet to dc\.

Second important mechanism of quenching is nonradiative transfer of electronic become equal t o interaction radii ( r = independent of molecular dimensions. The quenching of fluorzscence by added substance Q a t concentrated expressed by the Stern-Volmer equation.E 3C I time of the donor. cule can interact with another molecule to bring about a physical or c I : ~ . The ol~ticalcollirion. 3 Physical quenching of Hg-resonance radiation by added gases may occul. F o r a molecule in the excited state. (iii) form a photodimer. This into (i) Coulomb term and (ii) exchange term. the efl'ective cross-section for coi.+ A-At and charge resonance state AA* e A * A . the fluorecsence intensity F is linearly related to thr conc~ntration01 the fluorescer as where +. (ii) k2 = 8 RT mq 1 m01-I s-1 (sliding friction . $Ql= 1 + Ksv [QI where + . 10. are fluorescence quantum yields in absence and In presence of and pel is the electronic interaction energy parameter which can be broken up quencher respectively and Ksv is the Stern-Volmer quenching constant. If I. into original molecules. Oxygen may form C T complex and lead to peroxide formaticn in the triplet state. Ionization potential of the donor.~ for excimer formation I S provided by interaction between charge transfer (CT) be defined as the ininirnum distance of approach over which the excited r. Those systems which give 2 . and (ii) exchange interaction responsible for short range transfer. nonradiatively or lcad to reaction (iv) by complex formation in the excited state leading t o chemical reactiorls or products. 7.aiisferi. - RAB is the encounter radius. (ii) dissociate nonradiatively theory of gases. For such 13. The rate constant k.and r D are respectively fluorescence efficiency and actual radiative life- F ~ 4 ~ 2 I . excited state. Z<xD* I xD > < xA* I XA > l2 +f =1 ik. If added substances absoroinp a t higher frequencies arc present the quenching number of mechanisms: (i) transfer of electronic energy to the addec mechanism is visualized t o proceed through transient complex formation in the (E + E transfer). Due to Franck-Rabinowitch cage effect they occur in sets called dissociation is through electron transfer between the excited molecule and the 'enco~mters'. Exciplexes may decay radiatively. and the Ilfe' 16. then F the acceptor. the molecules can approach as c l ~ as\ ~ in the excited state and thus differ from the excited state o f a dimer. The blnainp energy can be much greater than those for kinetic collision. The rate constant for long range transfer by dipole-dipole mechanism is given by time of the fluorescer r in absence of the quencher. and 4. Spin selection rule applies t o such transfers.. In concentrated solutions. quencher. 12 When the quencher contains heavy a t o t ~ nonradiative ~s relaxation of the exciple. The expression for rate constant for transfer is similar t o the one derived for nonradiative processes within a molecule [QI 6 . This must be differentiated from static quenching. concentration quenching may occur. their van der Waals' radii and they are said t o be in collision. where DA and DBare diffusion coefficients of the two colliding partners and 14. mechanisms: (a) cnarge transfer mechanism and (b) energy transfel mechanism. electron affinity of the acceptor 5. constant is the product of birnolecular quenching rate constant k.a 11. A special case of this equation is when Stokes radii ~ rB a). is kept constant. energy of activation AE is negligible a n d steric effect is absent.i!c. '!. 9? rise to photodimers may not decay by exclrner emission. character. Theconcentration quenching is said to proceed via intermediate formation of excimers by inter- 1. +O is where F. In an ideal be wavelength independent. In ground state. There are two types of interactions : (i) dipole-dipole coupling interactions leading t o long range (sliding friction # 0) transfer.. For dilute solutions. state A+A. . ~EIOTOPHYSICAL KENETICS OF BIMOLECULAR PROCESSES 209 Summary 8. Collisions in solution are diffusion-controlled and hence depend o n the viscosity occurs via the triplet state (heavy atom perturbation).. The primary condition for a bimolecular reactlon is the 6close' approach of two action between a n excited and a ground state molecule. where r is unaffected. A second mode of exciplex of the solvent. Paramagnetic ions of the transition series and lanthanides also quench the triplet states. They are knownas excipI~.. Paramagnetic molecules 302 and zNO are very efficient quenchers of singlet and favourable cases kl is expressed by the equation triplet states.. . 9. K is an orientation factor and the integral defines the overlap between the fluorescence spectrum of the donor and the absorption spectruru of where the symbols have their usual meaning. Excimer may relax (i) by emission of characteristic structureless band shitted to of collisions between unlike molecules and like molecules are given by kijIcric about 6000 cm-lio the red of the normal fluorescence. 4.. .2. This is known as a n excitation spectrum. Quenching by added subvtances generally occurs throupll two broad-babe(: change. The rate constant becomes energy from the fluorescer t o the quencher.). radiative return t o the ground state.ic. (ii) energy transfer in the vibrational modes (E -+ V t. for birnolecular reactions becomes encounter limited if and solvent dielectric constant are important parameters in such cases. The transfer probability is usually expressed in terms of critical a function of wavelength will reproduce the absorption spectrum assuming 41 '' transfer distance I.:.frr. the Franck Condon factor . For such transfers the energy level of the acceptor should be equal t o o r lower than that of the donor and some donor-acceptor coupling interactions should be present.resand have pronounced charge transfer (iii) dissipation of excitational energy as translational energy ( E -+ T) tra. 0) IS. The frequcrl. Excimers are stable only interacting partners.

If the chemical change occurs on the same con- tinuous potential energy surface. providi: means for populating the long-lived triplet state to which transition\ . migrates from solvent to solvent until it is captured by the s o i u : ~ molecule from which emission may take place. The phenon~e~loir is known as delocslized excitation or c~. electronic wL~vl:functionsspatially overlap. the intermediate case certain fractions of the reacting species n l a j acape deactivation long enough to attain the product configuration. situation R.ion-con::. it is classified as diabatic. excitation energy. before the product configuration is achieved. These arc much greater kinetic encoiiritcr radii. The rJte follows diff~i. cxchange mechanism occurs when donor and ac. Gdt3 and Dyt3 emit line spectrun. 17. But the majority of photochemical reactions in condensed phasc produce product molecules in the ground state indicating a radiationless transition from the to a lower potential energy surface of the system before the chemi- cal reaction is completed.1 CLASSIFICATION OF PHOTOCHEMICAL REACTIONS A photochemical reaction may be classified as adiabatic or diabatic. after decaying down to the lowest excited singlet state of t l i c solvent. and proton transfer in the excited state may be classified as adiabatic reactions. Short rarlgc tial?sfer bj..i f crossing of potential surfaces is involved.ucitort nligratiotr. in an adiabatic photochemical reaction the reactants dad products must correlate with each other and with the transition state. forbidden by direct absorption of radiation. In liquid scintillator. c .:c~.i:. The . hlultistep fast transfer of excitation energy may occur in ordered array of nlolccules such as molecular aggregates. Accor- ding to this criterion. i. depending on its course along the potential energy surface as a function of reaction coordinates. 18. the reaction is said to be adiabatic ...< i Tran\~f kinetics if doi:or. The products will be in electronically excited state and may be detected by their luminescence and/or photochemical properties. 19. Intramolecular transters between two chromphores separated by i n ~ u l a t : ! : ~ Photochemical Primary Processes groups can lend to absorption by one chromophore and emission from the other. Complexes of rare earths specially of Eut3. 7. SmfJ. characteristic of the central metal ion when ~tbsorptiontakes place in the liga!.e. i. The photodissociation of small molecules in the vapour state like I. vai. + + hv -+ I* I. crystals and polymers. There might be intermediate cases also ac illt~stratedi n Figure 7 . g SEVEN D* (1ril)lat) $ A (singlet) -t 1) (singlet) + A* (triplet) Such triplet-triplet transfers are very important in photochemistry because '::.i moeity. and acceptor e n e r g levels are in near resonance. forbidden by dipole-dipole rnecl~anisrnmay occur by exchange rnechanijm. .le of 5 nm to 10 nm are predicted.

state only after the rates of other competing processes are identified and (c) Diabatic reaction-ground state products. sum of rate constants for deactivation of Af. except by photoreaction. If A. s). 10 I =rate of absorption = rate of formation of A:. These rules may be influenced by local forces at the point following general scheme can be drawn up for the reaction to occur from of intersection. measured. A* -% .] -k---- br~:1= 13 ' kc + k ~ (kc I- +k kb ~(ko ) + kb) . of the same Figure 7 .~ E x c ~ r c dstale poducls Figure 7 .2 RATE CONSTANTS AND LIFETIMES OF REACTIVE ENERGY STATES For a photoexcited molecule. The seat of photoreaction may not be the initially excited state. rate of reaction IR rate of absorption of radiation . free radicals. general. or less when the reaction step must compete with other photophysical processes. by applying the steady state singlet and triplet states. is the initially excited molecule. Rate k. where A t is not the initially excited state but reaches subsequently by momentum and symmetry and the selection rules for radiationless processes photophysical processes. An important aspect of photochemical studies is to establish the energy state involved in a given reaction. The photoreaction can be unimolecular such as photodissociation and photo- isomerization or may need another molecule. A*-t-13 ---t P kr [A*][ B ] (bimolecular) k ~ rate = constant for formation of the product. The quantum yield of a reaction can be related to reactivity of a given (b) Intermediate case.2). Consider the reaction Af -+ P (product) crossing process is governed by the laws for the conservation of energy. 7. + _ [A. short lifetime . If the primary processes generate from initially excited state.212 FUNDAMENTALS OF PHOTO CHEMIST^^ fl0nX:HEMICAL PRIMARY PROCESSES 213 The efficiency of a photochemical reaction is defined (Section 1. usually unexcited. they may lead to secondary processes in the dark.respective concentrations are obtained.I x fractional absorption s-I cm3 A d ~ a b a l ~reactbm c Inlermed~arecases D n a t a t ~ cr e a c i ~ o n Ground stale produi I s . time . (a) Adiabatic reaction-excited state products.2) in terms of quantum yield of reaction (PR.kb unpaired spin. actions such as spin-orbit coupling and hyperfine coupling. =sum of rate constants for deactivation of A: except by transfer to A:. (ii) vibronic interaction or Franck-Condon factor. which include (i) electronic configuration interaction.moles of aroduct formed or reactant consumed s-l ~ m .1 s) for the reaction and greater reactivity due to their [A:] -. whereas tripiet state has less energy but more I.. then the are applicable.~ potential energy surfaces. the time allowed for a reaction to occur is of the order of the lifetime of the particular excited state. 2 General scheme for a photochemical reaction which does not occur or differznt kind and hence bimolecular. The singlet excited state has more energy but aP~roximation. 1 Classification of photochemical reactions according to the nature of einstein absorbed s-l ~ r n . k.------ k a 4. the photochemistry is observed to occur from lowest excited Since the lifetimes of excited states are small. and (iii) magnetic inter- A: (Figure 7. C + D kr [A*] (unimolecular) kb = rate kc= constant for crossing over to Af.

for unimolecular reaction The reactivity of the given excited state can be obtained by simply kh . initially excited state under the actual experimental conditions. then for 3. 1 4 ) from the primary excited state and whose quantum yield is not unity. the quantum yield '#R is given by less processes. For bimolecular reactions. Let us consider a general scheme in which a reaction may occur from if there are a number of states through which the initially excited molecule either the initially excited singlet state o r the subsequently populated has tumbled through to come to the reactive state.~HOTOCHEMICALPRIMARY PROCESSES 215 4.8) = rate constant x lifetime x product of rate constant A + / I v -+ 'A" 1. and the rate constant k~ as lA* -t 3A k ~ s [lA*] c 'G*+B-+ C+D ['A*] [Bl 3A -t A k ~ s ['A1 c It is evident. the quantum yield 3 f $ is~ given by 3 k [Bl ~ krsc 34R = ----u k. . Assuming no emission from the singlet or the triplet states. 1. is expressed as we have Rate +R = k~ TAT ~ ~ J T J (7. kb. In the general case of a first order reaction which docs not occur = 0. ' ks t~ lo9 1 m01-1 s-1.---la measuring the lifetimes o!' that state at two different concentrations of [B]: Rate = k~ [A*] = k~ (7. In general. 1. which themselves are composite consisting of radiative and radiation. physical quenching and chemical reactions other than that of direct interest. are the lifetimes of reactive state and the efficient in product formation than a long lived state of lower reactivity. A short lived state of high reactivity may be less where rA: and ~ ~ respectively 7 . that the determination of specific reactivity of 3A+B + C+D 3ka 13A:IBI a given excited state involves the knowledge of several quantities ka. The following specific cases can be identified.. kc etc.4) dt we have. and if kjc: is negligible 2nd klsc = 9 x lo8S-'.5) kc -tk~ ka -tkb ~R[A:.1 M. ' k [B] ~ Arc + klsc lka [B]+ = l k ~ [B] where 1 7 is the actual life of the singlet state. for triplet state Af = A: reaction. d[P1 dt = kR [A:] unimolemlar reaction (7 3) d[Pl = kR [A:][B! bimolecular reaction (7.T.15) For a reaction in solution occurring at a diffusion-controlled rate. k~kb and IR. Similarly. experimental determination of the rates of radiationless processes and of the quantum yield of formation of reacting electronic state becomes ff the same reaction occurs in tne triplet state with reactivitv about necessary. a knowledge of the concentration of Since the rates of formation of ~ r o d u k tare given by: B ISrequired. ~ I S C (7. the efficiency of singlet state reaction is (equation 7 . p + %R [B] +kc: ~ I S C 2. then reactivity as defined triplet state.7) of the particular state. . + + (kc k R )(ka kb) Therefore. For singlet state reaction. the limiting pararjlcter in all reactivity studies is the lifetime = ( k ~ r )~( rkb ) (7. lk . by quantum yield +R. for reaction of reactive and lifetimes for all the IA* + A klc ['A*] state higher excited states. If the reaction occurs entirely from the state reached by absorption. therefore. If the quantum yield of rejction is unity and the reaction is simple = ' k [Bl ~ 37.

The slope KQ will etc. then asain hathis simplified scheme. a plot of The quantum yield for the primary photochemical process differs from that of the end product when secondary reactions occur. In this case the triplet state of the photoexcited reactant is the by four orders of magnitude. Where secondary reactions are set up. and assuming F p -- $Isc 1 and k&. etc. Rates are usually directly Pro~Ortionalto the light intensity.~ I S C$.2). 1 d 1x1 . + kR [B] kR lBl M ~ n o ~ h o t o n iphotochemical c reactions are those where each absorbed = 41sc + k&c k~ [Bl Quantum excites one molecule which then reacts. High quantum yields are due to secondary processes. s. kAC 4.k f kg. The actual lifetime of the singlet state IT. works out to be -. k~ [Bl The quantum yield of photochemical processes can vary from a low 30n=41sckTISC + k~ [B] + ~ Q [ Q ] fractional value to over a million (Section 1. depending on tho chain termination Processes. If the experiment is repeated for a set of reactant concentrations [B].Llb FUNDAMENTALS OF PHOTOCHEMISTR~ 217 OCHEMICAL PRIMARY PROCESSES lo4 times less than the singlet state. reaction is expressed in terms of quantum yield of disappearance of the reactant or the appearance of the product '33 EFFECT OF LIGHT INTENSITY ON THE RATE OF #.). NMR. then 7 can be estimated and since 7 . 2 for a bimole- cular reaction. A low quantum yield for reaction in solutions may sometimes be caused by recombination of the products due to solvent cage effect. species produced as intermediates can only be studied by special techni. s and that of triplet state to be -.1 M. 3 k = ~ lo5 1 mol-' S-'. From the i+Gept Qsc can be obtained and the slope/interccpt ratiois k&/kn.". ESR.15) @@tant for the reaction k~ can be estimated by the method of competition. reaction is carried out in presence of a third substance which quenches reaction physically or chemically by competing for the reaction inter- In this hypothetical example.0 A Stern-Volmer type expression is obtained. Assume that the reaction occurs from the triplet states k&c and kR can be calculated from the slope and intercept of the linear only and step (4) is reelaced by fluorescence emission step. For nonchain reactions.= 9 x lo4 s-'. a commonly observed value. If kQ lis considered diffusion-controlled. (equation 7.A R [Bi -b k~ [Ql -- yields for various competitive photophysical and photochemical processes $R kk. If chain intermediates are terminated by unimolecular reactions. 1 Determination of Rate Constants of Reactions Consider the reaction scheme as given in Section 7 .c kR [Bl PHOTOCHEMICAL REACTIONS Ia dr k r ~$. the quantum 4-. k1. . IR. Transient &/#R vs [Q] will be linear and the slope is equal to KQ. rotating sector devices. The short lifetime 'A+Q 3 A+Q k~ L3A1[QI does not allow enough time for reaction even though the reactivity of the expression for the quantum yield of reaction becomes state is high. set of straight lines of unit intercept will be obtained. aithough the triplet state is less reactive d i a t e . An initially excited molecule may start a The ratio of quantum yields in presence and in absence of quencher is chain reaction and give rise to a great number of product molecules before then given as the chain is finally terminated. 2 . At constant [B]. Suitable spectroscopic techniques can be utilized for their observations k: a function of [B] (UV. + k~ IS1 must add up to unity for a monophotonic process if the reaction occurs from the singlet state only: $R+ +$f 4 1 f~ ~ I S C N 1 . the net efficiency of reaction is the mediate and if the quenching step is same. a plot of [&]-I vs [B]-I should be linear. use of scavengers.1 --- 41sc +--1 kITsc + I S ~k~ [B] the changes. 1 . a ques such as flash photolysis. The rate of Plot between l/KQ rs [B]. Therate for [B] = 0. where T is the lifetime of 3A in absence of quencher.---.

and. 4 TYPES OF PHOTOCHEMICAL REACTIONS The chemical behaviour of molecules generally depends on the most weakly bound electrons. 7 . Because of their long life. Type I c 7. the molecule may be more easily dissociated. different vibrational and rotqtional modes may be excited which can bring about reactions. more commonly. is more likely to be removed by an electrophilic reagent (oxidation). (3) The excited electron is usually in a more weakly bound orbit. but if atoms or radicals reconlbine to or more than the bond dissociation energy. and provide a mechanism 4kinetic energies may impart increased chemiccl activity to the photo- whereby high energy bond cleavage may be effected with lower energy fiagmented particles. as soon as the orbit begins to overlap with that of the excited molecule due to increase in electroc affinity. If excited to the repulsive state dissociation may occdr with unit efficiency (photodissociation).1). (2) Because of the Franck-Condon principle.1 Photofragmentation or Photodissociation Figure 7 . 3 Situations for predissociation o f a diatomic molecule on photoexcitation. and HI light is interrupted by a sector disc rotating at different speeds (Section les. echanisms are best appreciated with the help of potential energy mediates may be obtained from the variation of rates when the incideRt for diatomic molecules as given in Figure 7 . At very high intensities biphotonic reactions are encountered. rates vary as 41. normally not poss~Mein the ground state (valence isomerization). often extending over a larger region of space.3. The direct dissociation of a molecule o n absorption of a q u a n t w of .9). The symmetry correlation rules are helpful in photons. a redox reaction may b: set up by intramolecular or intermolec~la' electron transfer processes (redox reactions). phtolysis. A molecule in the excited state differs from the ground state molecule with respect to both energy and electron wave- function. (5) In inorganic compounds or complexes with variable valence system. triplet :*a partners which fly apart if in the gaseous state.4. A molecule excited into the continuum region of the absorption 10. or. 4 for C1. and therefore differs in its chemistry. therefore. Such photodissocia- bimolecularly. Any excess energy will appear ss the kinetic energy of Rates here become proportional to I*. @ excited state. w w u m dissociates immediately with unit quantum efficiency.as with vessel walls or with other molecules t o give relatively stable pro. In such a case it is possible that at least one of the atoms is in reaction occurs by the interactions of two excited molecules (Section 5. nal energy becomes very probable when the energy absorbed i~ ducts. In this latter case l~fetime of inter. either tw When the molecule dissociates from an excited state it is called quanta are simultaneously absorbed by one molecule. The excess potential states are involved in the second of these processes. (4) The excited electron may interact with any other odd or unpaired electron attacking agent and form a bond. Irradiation to produce an excited electronic state alters the reactivity of molecules in a number of ways which decide the nature of any photochemical reaction: (1) Since nuclei are often more weakly bound in the excited state than in the ground state. rates are proportional to I.

H + . and H. . The (Figure 7. The . NO photoreactionoccurs between I. (ii) in setting up the reactant-product symmetry correlation rules it is not fP&tion initiate a chain reaction by abstraction of H from H. The exotherrriicity of reaction between Br + H. + hv ---+ 2C1 (iii) the energy states of the same symmetry do not cross (noncrossing rule). They are called hot ru'iiculs and have enough energy to propagate the chain. Cl atoms generated by photo- the symmetry of the products must correlate with that of the reactants. I + . rates vary directly as the intensity 3fradiation I. In highly purified gases and large vessels the reaction A. and H.Cl + . The chain termination by the visible and near ultraviolet regions associated largely with nx -+ 0:-.l r r lo5. a1 PI 11 Liie~ 01 ( I Pblen el ur I . Evidently the molecules are excited to the repulsive part of the upper electronic state resultingin dissociation with unit quantum + H B ~= - HBr/rate dt of light absorption efficiency. Chain termination is continuum where one of the atoms produced is in the excited 2P.. + C12 -+ HCl* CI+ AH--. ?xpression for quantum yield of HBr formation + H ~ rcan be set up from The absorption bands of H I beginning a t 360 nm(h. is 1:s~ and therefore smaller chains are produced whereas + 1. H + AH=4. 5 11 .).. These rules are: (ii Fin gaseous mixtures of H.. H + H I -t H z + . Thu. +H. Here the rate varies as l/f. becatrsa of ~ i i : poor reactivity of I atoms. Figure 7 . I -+ 1.ng I T ) :hekc reaclic. The high Termination: . H + M -+ EQCI+M transition leads to dissociation into two unexcited atoms.2 W surface (adiabatic reaction). as O2 present in the system. H reaction is endothermic (AH E $ 38 kcal) and no chain reaction is Possible.X. holecular atomic recombination is associated with a third molecule to type transition where R may be a halogen atom or a hydrogen atom. The abstraction of H from H. 4 Potential energy curves for CI. Ihz radicals are Produced with excess energy. and CI. M energy transition is lIIlUt 12: and is continuous at all wavelengths. The The reaction between Br. state mostly by Br atom recombination.Cl is thermoi~eutral(AX! = 4 2 hJ) but the next step is highly exothermic (AH =. #move excess energy. The transition promotes a nonbonding electron localized on the halogen atom X to an antibonding energy level of the molecille R . HI+hv -+ .I = 2. and HI molecules. +. Gas phase photolysis.Cl + M -+ + Cl. The spectra of pditions. I 5 r ~ A i J . X(2P3/. scopic continuum region if a higher energy state intersects the curve at a rednation of the chains of this reaction is very sensitive t o experimental suitable point creating a dissociative situation (Figure 7. = 218 nm) is lteady state approximation : completely continuous. needs a somewhat elevated tempera- transition 311L t is partly structured and converges to a second ture because of the weaker reactivity of Br atoms. 189kJ Photodissociation may occur even on excitation to below a spectra. .: X 478 nrn possible to leave a lower'energy state of given symmetry uncorrelated. and Initiation: Cl.~ls.189 k3). by .. Thus reactants and products must lie on the same potential energy propagation : CI + H2 4 HCl . If atoms are removed by wall effects or by inhibiting molecules halogens and halogen acids are instructive in this respect. I Po e . The halogens and halogen acids absorb light iI1 . the quantum yield fop photodecompovition Of Hl.Cl+ . These results emphasize the impor!ailcc: of rnergy changes involved in bond breaking and bond mak. On the other hand.hains may be as long as lo5.4). 226 FUNDAMENTALS OF PHOTOCHEMBT~~ predicting the energy states of the product particles.3). giving a l/r rate dependence..

.2.)and m e in the excited state fragmented into alkyl radicals and nitrogen The excited I(2P. The atoms are deactivated by encrsy t r a ~ ~ f eoil with oxygen n~olec~~les generating si~iglotmolecular oxygen. Another system in which laser action was observed is the photolysis of CF. In presence of unsaturated compounds. C X ~ R .NH -+ H. C X ~ R . merges intoa continuum beyond 175.+'CONH. ----+ 4CHBr CHBr COOH Ilr 'he groulld btate oxygen atoms react with oxygen molcc~ilesto give ozone .C + Brg (CH& CCBr = CHBr CH '-3 0:s2iD)4-O.(X 3C. RCH2NHz+ hv RCH. Usually chloro.CF. X. It + R . The laser action originates from electronically excited I* atoms..7 km. molecules by suitable wavelengths gene. The photodissociation of I.9 nm and correlates with one oxygen atom 0 (PP) in the ground state and one in the excited state 0 (2lD) The reactivity of halogens in such addition reactions decreases in the > > order chlorine bromine iodine.F+H.6 nm and is called the Schumann-Runge band system (Section 2. This type of laser is termed a photodissociation laser.-% RCO + NH. = CHCl + C1. The active molecule is born in the excited state. -t R .+ HBr--+l1v CH3CH.H AH=.1).CH2Br to give vibrationally excited HF* or HCI* in large numbers.:(X :?. r hv (CH. I emitting at 1. CF.CI CHCI. C . These systems emit in the infrared region.NH. is B 32i t X3C. Since there are no vibrational and rotational modes in the I atom.139.CH CH.CH2CH3 --a K. The photodissociation of oxygen in sun- light is the major photochemical process occurring in earth's atmosphere. pumped.r. CH r CH + H Br+ 611. + R2CXCXR. -----+ O(YP) O(2'D) + - are produced by this method : O(2lD) atonis arc nietastable and haie ~ e r ylong life in the thin hv CH. -+ RCHNH.+*CH. 1% .9 kj to synthesize alkyl and alkenyl bromides is also exothermic and can produce energy rich HF* molecules.+. chain reactions can be generated by haiogen atoms. which occurs at X + R 2c = CR.9 O.CH. Emission iiv from these hot molecules can be obser~ed in the infrared region at A 3. + X. -+ R. They had termed such a system as photoexplosion laser. + I (aPl12) CH3CH. ---+ CH.H + HI + CH.CH3 + HI + . the efficiency of I* production may be 100%. Atomspheric plrotocl~emistry. x. without any external source of radiation.:') hv 40 CH = CHCOOH + Br.222 FUNDAMENTALS OF PHOTOCHEMISTR~ ~HOTOCHEMICAL PRIMARY PROCESSES 2 23 The reaction The photoaddition of hydrogen bromide to olefines and acetylenes is . + ~ ( 2 ~ ~ 1-i ' )0 2 ( l )I.) has enough energy t o abstract H atom from a Amides and amines give a variety of products: hydrocarbon in gas phase reactions RCONH. the main fragmentation process results in the 3. atmospl~ere. For photohalogenation reactions B.315pt?z. % 2 x .8). Laser action in these systems was first observed by Pimental and Kasper in 1965.. The laser is chemically &ination of hydrogen.compound^ hv(175. The heat of chemical reaction is distributed in various vibrational-rotational lnodes CHSC = CH.). The first intense allowed transition in 0. + HF*+. 202. They are known as chemical lasers. I* + -t RCH = C: + H. = CHBr The reaction systern in which partial liberation of the heat of reaction can In the vapour phase photoiysis of hydrocarbons in the ~ucttut~z UV generate excited atoms or molecules is capable of laser action (Section region (120-200 nm).and bromo. Azoalkanes when phoeolyzed in the vapour phase are readily rates one I atom in the ground state I (52P3r.

Photolysis of N. The possible O(lD)-+ O(3P) ! hv(A = 620 nm. atmospheric NO concentration M in a number of steps : is high but after sunrise.(32. Ozone has weak and diffuse absorption throughout the visible region and even in the near infrared. M + NO. Two oxygen atoms can also recombine to form 0.) + -c = c-c -+ .. The . -+ RCO. but: a t i a liable t o meterological conditions of 'atmospheric inversion' are at h = 264 nm. R'CH.) 253. ) 11v(h= 762. + KO. acrolein and peroxyactyl nitrate (PAN). In cities with n~anyindustries and +M RH - 2 Hg(6lS0) + M +M (c) collisional deactivation Hg (@Po) S-bI(d) collisional deactivat~on to 63P.(lA. ) -+0.n a vibrationally excited state which must be stabilimd by a third bodv sulphur compounds..r \ c o 3 mechanisms. ) -+O(23P) + O. C . NO decreases and NO. (32..4 nm) reaction sequences are : O(IS) -+ O(3P) + hv(A = green line) o.'A. -t 0. formaldehyde.7 nm The maximum quantum yield for decomposition of ozone at low pressures 7 Hg (6's. Formation and dissociation of ozone is one of the important RCO + 0. Mercury atoms are frequently used as ~hotosensitizeoin vapour phase reactions. and small aliphatic hydrocarbons (alkanes) set up complex reactions in the upper atmosphere. etc bands suggesting photochemical control of the concentrations of these species. ) + hv(h = 1270 nm) OOH + 0. the life would not have RCO. state --+ Hg(6lS0) t. molecules: 2 O(2.) -+ .c-c- H 1 0. The mechanisms involved are O(2lD) + 0.NO. + RICH. appedrs. the atmosphere is polluted by the smoke coming out The main . RCO. In the early morning. NO. some is produced by photolysis of water vapour in the vacuum ultraviolet region h (200 nm. NO. by photochemical reaction between NO and 0. excited O-atoms are produced: Specially subject t o smog trouble. -% N O + O The emission from electronically excited atomic and molecular oxjgen is the cause of the night airglow. D.) Hg (6'P1) is 4. CO. I'he ozone is depleted by this reaction and is regenerated by reaction with O-atoms.O + NO.M -+ 0.(3Z. CO. PhoioelzcrnicaI Fonrzotion of Smog. f NO -+ 'RCO. (e) radical formation automobile traffic. Hg PI) Hg (6lS0) + hv + (a) resonance radiation Though most of the oxygen in the atmosphere has been formed by +Hg (6lS. No29 NH. ' 0. is forrned r)(23p)+ o t ( x 3 2 . The steady state concentration of ozone in the upper 'RCO. atmosphere is very small but it absorbs so strongly in the near ultraviolet ' RCOz + NO + .cmospheric glow originates in the upper atmosphere where the pressure is so low that the radiative decay can Three specific eye irritants have been jdentified in photochemical smog: compete favourably with the collisional deactivations.R + [I. Without this shield.ONO. (PAN) emerged on earth from under water where it is thought to have originated. + NO 3 RfCH.Pj -i.Mercury photospnsitized reations. Absorption in the visibie region decomposes RICH.) + A* (h) energy iransfer +A photosynthesis in plants.O. . NO and some i.RCO -1 NO. "HOTOCFIEMICAL PRIMARY PROCESSES 224 FUNDAMENTALS OF PHOTOCHEMISTR~ 225 components of the smoke are unsaturated hydrocarbons. (alkyl nitrate) ozone into oxygen atoms and molecules. 636.O. -t RfCH.0 nm) There IS sharp variation in night and daytime intensities of these + rddicals.(lA. that it screens the earth's surface from the light of wavelength < 290 nm which is deleterious to life.lLY. + 0. + NO.c. both in the ground state.(32.

-> (CkI. . and a photosensitizing dye.7 nm.C = CH.effectively a single bond. 4 HgH H + \N=N 'CH. ~. observcd for relaxed triplets: The degradation can be photochemically induced (a) homoiytic or (b) heterolytic cleavage a t the weaker bonds.H2 (a) may lead to elim~nation reactions and the type (b) may lead to free + CH.Cld. i. The singlet oxygen formed as an intermediate is the reactive species. and N. The quenching crosssections are large for compounds having are harmful t o biopolymers like DNA.~ 1 4 : -+ HC z CH -1.. fragmentation occurs produc- + ing molecular nitrogen and alky: radicals.=CH*'H* radical formation The point of bond cleavage may not be the seat for light absorption. 7. Photodegradation of polymers: Photodegradation of polymers assumes are expressed as quenching cross-sections for mercury phosphorescence at importance in two different contexts: (i) ultraviolet and visible radiations 253.) olefin 4 Hg (IS.2.. Cis-trans tomerization.entcage.CH3 The first two are of minor importance. and low lying triplet states. -t CH.4. ( 2.CH. cotton fibres undergo photodegradation by rather complex reactions. the reactton proceeds through cornpiex bond becomes possible. Starting from any given . .C With saturated alkanes and NH. -1-11 The possibility of free rotation facilitates cis-trans isomerization and ljg* -t (Ct-I. N.5). -. are prcsentcd in Section 6. 6 . The planar molecule obtained from Franck-Condon format ioll relaxes to a configuration in which two -CH2 groupr are * *I -+ I + t l g -L NW. N i t .2 Isomerization and Other Rearrangement Reactions A. H.)2C)-1. In this state.H~TOCHEMICALPRIMARY PROCESWS Hg (63P0)cannot return to the ground state Hg (6IS. With olefins. C2H4 + (dimer) In presence of 0. The lowest acited state of ethylene results from excitation of a x-electron into an mtibonding x*-orbital. (process (b)) from T1 and Na vapour deactivation of initially produced vibrationally excited hot molecules.C bond .. -+ 11. Phorodissociation reactions in transition is doubly forbidden by the selection rules J = 0 f i J = 0 atld liquid phase occur at much reduced quantum yields because of the AS # 1.[tv PeQendicular to each other giving rise to a diradical (Figure 7. Thus Hg (63P0) has a very long radiative lifetime and can be possibility of recombination within the sol~. the solvent may react with by CO. = Cl-4. the possi blc photochemical reactions are When azobenzene vapour is photo11 zed. product fornlation and distribution also differ because of collisional The mercury sensitized emission.. Photofragmentation in the liquidphase. In presence of the ionic species.. -+ Hg (63P. i .) + 3olefin (v) 0:hot olefin triplets) The relative reactivities of various substances towards mercury triplets F. free rotation around C . + Hg (6?P. The large alnount of vibrational energy an understanding of their mode of photolysis is important in life processes accompanying the transfer from such energetic species yields 'hot' triplets and (ii) more and more use of plastic materials in everyday life has created which possess many interesting modes OF decomposition norlllally not a problem of disposal.O. but in liquid phase the main - Hg (h3P1) -t H. Consequently. the bonding effect of n orbital is %celled by antibonding effect of x* orbital and the resulting C . The photolysis of the type Hg* { . etc. 6 . has been discussed in Section 6 .) by emission since the E. The quenching to 6V0 (process (d)) Where CT absorption produces radical ions.). NH. proteins. I-ig* Can be demonstrated in substituted ethylenes. polysaccharides. . Furthermore the deactivated mainly by collisions. . The energy can 111igrate from unit t o unit until it finds itself at the seat of reaction. The simplest molecules which can undergo cis-trans isomerization are derived from ethylene H.) Hz -t ~g ( 6 ' ~ ~ ) H. + reaction is isomerization : -+ Hg (6lU 2H} = + CHB vapour + N.

. the centre in the diradical configuration but the ground state rotamers are Tbc energy of the perpendicular triplet state is expected to be low since in rapid equilibrium. r*)state because of migration of the double bond in cubr triplet state and was termed a phautoni triplet state by Hammond. cis-irons isomerization in the excited stale their planar geometry. A common (n. 1. FUil efficiency. TIand S. A photostationary equilibrium Studied in detail by Hammond and his group and it has been found that is established. increasing the number of f i e perpendirular triplet state can be directly populated by energy 1 otermcd . In phenyl substituted ethylene. states as a function of twiit angle W + h c * (trans) is liven in Figure 7 . Deactivation of molecules from this Can give either the ground state of cirisorner or the ground state of tws-komer depending on the mode of rotation. 5 ) '%let state in 90" configuration. Qthis configuration the overlap between the n and x* orbitals is minimized. 4-butadiene. trans HOMO L UMO H ~ g h e s or c c u p ~ e dMO L o w e s t u n o c c u p ~ e dMO CIS ( b) Figure 7 . rotation is considerably Intermediate in each case. The ground state (I) and the lowest excited state (11) MO's in transtilbene are indicated as HOMO wilest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) in Figure 7. Figure 7 . This triplet state ic referred to as the pcrpc~a'i- restricted in the (x. . potential energy of So. -3 l ( c.3 butadienes are well known to undergo such cis-trans iromerization as primary photochemical processes. In either case moliculer In the next higher vinylog. 7 fast fJ JT S I ~ A . (b) trans-cis isomerization in the excited state. the corresponding rotational isomer can be produced on The photosensitized isomerization of ethyle~esand stilbenes has been photoexcitation by suitable wavelength.6. differing from the thern~odynamic equilibrium of the in each case both the cis-tram and the trans-cis isomerizationc occur with ground states. FUNDAMENTALS OF PHOTOCHEMETRY ~ODTOCHEMICAL PRIMARY PROCESSES 228 Franck-Condon + .x * ) triplet state is assumed to be the For the next higher polymer. f e configuration. stilbene +CH=CH+. The perpendicular triplet state T can even be lower than the ground /-h. 5 (a) Franck-Condon x -t x* excitation of ethylene and subseyucnt A photostationary state cis-trans equilibrium is established on excitation relaxation. the central x-system cap conjugate with the phenyl n-orbitals. of either cis-or trans form of stilbene on promotion to the S. r gain becomes feasible around each single bond. configuration.'excllatlon of ethylene and subsequent relaxallon 1. 6 Nodal properties of HOMO and LUMO of stilbene. state.

3 migration) in structures of the @owing type: . P IIBMICAL PRIMARY PROCESSES trans Angle of t w ~ s t CIS trans P erpend~cular t r ~ p l e tstate L ~ S For butadiene. quench the triplets of suitable sensitizers by energy transfer with u s t aciency. specially 1. 5-hexadiene perpendicular triplets is termed a nonvertical transition. Tl and Sl states of ethylene and (b) its electronic configuration. For example.3-pentadiene (piperylene) and hexadienej Compound (B) from triplet state. they are used widely in mechanistic studies of photo* chemical reactions. I a1 ( bl Figure 7 . B. transition to e~clusivelyby suitable sensitizers. lhes a cyclobutene derivative (A) from the singlet state and tricyclo ring The dienes. two photochemical cyclization products are cyclobutene o r bicyclobutane. Sensitizers with . In such cyclization. transfer from a suitable donor without having to pass through S. Therefore. The triplet states can be populated Condon principle of vertical excitation. as a function of twist angle during trans-cis isomerization. This leads to clean isomerization without the complications of photoproducts from these excited states. aeited singlet state or the triplet state. Hence. valence 1. on rxcitation Photo-~riesreorrangernent: Photo-Fries rearrangement involve migra- pentadiene. 3-methylene-I. Extensive studies of sensitized cis-trans isomerization has confirmed its existence. either to count the triplets or to establish the triplet energy of a sensitizer whose ET is not determinable from spectroscoPlc data (chemical spectroscopy). The conjugated polyenen rn their excited biradical state can lead to intramolecular cycli~ation in a number 3-methylene Sens. For example. 5-hexadienc bonds are reorganized without migration of atoms or groups but migration of D or z electrons only. and T. the follosving products are observed: Yb of a group across adouble bond (1. Such endothermic transfer is not expected from dimes and trienes depends on whether the reaction occurs from the simple theories of energy transfer and also does not follow the Franck. Volenee isomerization. El cyclobutane energies less than the TI states of either cis-or trans forms are observed to In some cases the nature of the products resulting from photolysis of induce isomerization. states. ways oiving rise to a number of products. 7 (a) The potential energy of So.

N tion to its (n. 3 and 1. ~HoTOCHEMICAL PRIMARY PROCESSES 233 The oxygen atom of the activated alkoxy radical and the hydrogen to be abstracted and subsequently replaced by X. One of the prerequisites for the Barton reactlon is the availability six-membered cyclic transition state (where X = NO). R X-N I E. formation of dinie -s s b d such similar reversible reactions. Photolysis of liquid benzene by elcita- X. Pl2otoisornerization of benzene. RCH CH2 H P %$R RCHZ/CHL tions lead to states with quantum-mechanical stability but thprnmod! naniii RCH CH2 instability 'c' 'f '42 H2 "2 photochromic specic.7 nm -+ fulvene + benzvn1er.. rinq opening.200 rim --t benzvalene + fulvene + Deaar benzene. light i~lcli~ccd . tautomerism. stereoisomer~ctransition. Photochromism in solution and in the solid state can b: t h e result c#i 'ftramolecular changes. Photochrornisr~~or pf~ototropism. form two adjacent corners of the six-membered transition state. Some examples are given btlow. y FR. .free radical formation. . e. The major application of the Barton saction have been in the synthesis of steroids particularly with compounds involving functionalization of C.g.8). and C.. (2) excitation h 160 .e These rearrangements occur through intermediate formation of free radicals. 8 Photolysis products of liquid benzene under different excitation conditions (1) excitation A 253. Barton reaction F.x * ) states brings about interesting photochemical transform 2 3 ations from vibronically excited singlet as well as triplet states (Figure 7. In many compounds.H T4-i H ON reversible colour change is observed. Such light induced reversible transi- ?NO$~hV. cis-trans isonler~ra- b. Such rearrangements in aromatic systems lead to 1. H . D. which is difficult to achicipe in other ways. 5 migration The corresponding reaction for anilides is as follows: NHCOR NHz NH2 Figure 7 .

The MO description of simple aldehydes and ketones assigns a palr chemical high speed memory with an erasable image. Energies. Figure 2. the lowest triplet state. (q z*) and the corresponding triplet Tl(n. bianthrones). Such H-atom transfer may be visualized to occur first by transfer of an electron followed by proton transfer. T'hotochramic or phototropic dye stuffs are used as the basis of photo. There- fOfore in substituted aromatic ketones. the nature of substituent decides . x * ) characters : Tl = aT (n. 2-naphthoquinone-2-diphenyl 81 PHOTOREDUCTION AND RELATED REACTIONS hydrazone in polar or nopolar solutions The prototype of photoreduction reactions is hydrogen abstraction by carbonyl compounds in presence of suitable H-donors. n*) or even below the latter. of TI + So transitions as obtained from os?hnr~scence qpectra and the corresponding configurations of tbr: . intensity lasers.234 FUNDAMENTALS OF P~IOTOCHEMISTR~ t i ) Free radical formation in cooled solid solution of tetrachloro-I-0x0. x * ) .16). ET. x * ) state may bring 'the T ( x . A*) but the lowering of (A. x * ) igure 8.1). (n. In aromatic ketones. For thermochromic substances colour change is observed (Section 2. The lowest energy transitions are n -t x* and % + X* in which either an n or a x-electron is transferred to an antibond- on change of temperature (spirans. dihydronaphthaleae EIGHT Some Aspects of Organic and tetrachloro-I-0x0-dihydronaphthalene Inorganic Photochemistry (ii) Triphenyl methane dyes in MeOH + EtOH solutions N(CH3I2 N(CH ~ ) ~ crystal violet (iii) Ph~toisomerization of quinoid 1. x * ) + bT ( x . The low energy triplet state may bc a mixture of (x. in£! orbital. x * ) and T (n. x*) in the proximity of T ( 1 1 . % d e t may still be S. For simple aliphatic ketones the lowest singlet state is S.9. They can also be ofnonbonding electrons to the carbonyl oxygen which are directed in the used as automatic variable density filters for example as Q-switches in high Plane of the molecule but perpendicular to the C=O bond axis. An electron deficient centre is the seat of reaction and the efficiency of the reaction depends on the nucleophilic nature of the donor.

x*) and (CT) have different electron distribution. including benzophenone.COH + (C.n*) (a) If a suitable H-donor is present in the vicinity.---.CHOH -+ C.H~)~COH 2 (C~H~).. localized on O-atomto a x-orbital.H.T * ) . The dipole moment of )C = 0 bond is reduced.1. 9-anthraldehyde 40 ( 7 . (c. All the three types of excited states (n. hence exhibit differences i n their photo- chemical reactivity.COH3 (C.H. _ _ _ _ _ . For benzophenone in 2-pro- l-naphthaldehyde 56 (n. . -- A third possibility arises when an electron releasing substituent is suitably attached to an aromatic ring of a ketone.). the longest wavelength absorption is a low intensity n -t x* transition.COH. ( x .n*) panol as solvent.5 (.COH -t + (CH3)ZC= 0 (C. 1 Energy state diagram for benzophenone and acetonaphthone. wME ASPECTS OF ORGANIC AND INORGANIC PHOTOCHEMISTRY 237 42) For ( x . -- . The charge density on C-atom is increased TABLE 8. leaves behind a 'positive hole' on this atom.. -- Three primary processes are commonly encountered for this electrophilic - - Compound ET Tl centre : Benzaldehyde 72 (n. x * ) state in acetonaphthone.C = 0 (CH. x * ) state in benzophenone.COH (C6H5)2 . which 2-naphthaldehyde 59. promotion of a n-electron.COH + (CH.H5). producing a ketyl radical. B enzophenane In benzene s o l u t ~ o na t 2 5 0 ~ Figure 8 .i . The major contributing forms for these three electronic states are g i ~ e nbelow : (1) F c r (11.H~)~c= n*4. n*) can subsequently dimerize to pinacols. benzpinacol is formed with unit quantum yield. -0: 0: 1 I major contributing form -(3) For (CT) state in p-aminobenzophenone. In most simple aldehydes and ketnoes. The lowest triplet state of some aldehydes are given in the Table 8. d~ b~ benzpinacol At high alcohol concentration or high light intensity $R tends to 2. The charge may even- tually migrate to the carbonyl oxygen producing a charge transfer state (CT). the H-atom is extracted 2-hydroxy benzaldehyde 71 (4n*> by the excited carbonyl compound.).).).1 Energies and electron configuration of the lowest triplet state of some aryl aldehydes creating a 'bipolar' state. x * ) .(CH.

nature of the (CT) state. The presence of compounds with double bonds lead R \ ~ .. For a n + x * trdnsition. the charge density on C = 0 oxygen (a) (C6H5). In acidic media p-aminobenzophenone undergoes ready photoreaction . an axnine cation are formed in the intermediate stage.. (n. A switching of state energies charge transfer interaction between the triplet state of ketone and the in polar solvents occurs which imparts exceptional reactivity to this ketone.CH2CO N (CH& 4-6 -8 In the charge transfer state the polarity of the ) C =: 0 bond is actu'~ll> reversed. A ketone radical anion and It can abstract H-atom from cyclohexane solkent but not from 2-propanol..H5). arnines. to oxetane formation. One of the most striking confirn~ationsof the i. ---+ hv 0 OH (C.::lidity of distinctio:: between T. this compound. (b) (C6H5).C = 0 + RCH.i:::)state. The electrophilic C-C (C6H5):!f RCH = NR' (C6H5)~ character of the oxygen centre is decreased considerably leading to negli. it is observed that because of the l?ighly polal.n*) and T. there is a large solvent shift in the polar solvent 2-propanol. and amides. . 3s shown in the following scheme.6 *+ RC = 0 + R. The properties of these three types of excited states of aromatic carbony1 compounds are sum~narizedin the Table 3. Excess charge on oxygen niahes it inert towards 2-prop2nol. (CT) states is the effect of solvent on the reactivity of some of these compounds such as p-aminobenzophenonc. which lies very close to ( P I . x::) state to form oxetane (Patc~rtlo-Blrchireacriori) : -0: OH OH OH (c) Cleavage of the bond a to the carbonyl group produces radical A variety of H-donors have been used for the photoreduction of intermediates (Arorrish T j p e I clravagcl) : carbonyl compounds. They include amines. oxygen atom of the c ~ r b o n y lin the (11. The hydrogen OH OH abstraction may still occur if a weakly bonded hydrogen donor such as tributylstannate is available. 1 1 gible reactivity for H-abstraction from 2-propanol.NHR1 hv ---t increases due to the antibonding character of n* orbital. hydrocarbons. S ~ M EASPECTS OF ORGANIC AND INORGANIC PHOTOCHEMISTRY 239 338 FUXIIAMLN TALS OF PHOTOCF1L%lj)iR~ with 2-propanol since no charge transfer is possible in the protonated (b) A conlpound with unsaturated linkage can undergo addition with the ketone. R / ~ " . This brings about a lowering The photoreduction of aryl ketones by amines generally occur via a of the (CT) state with respect t o (n: n:':) state. From a survey of the energy states in 2-propanol and it1 cy~lol~cxane fo:. alcohols.4. C = 0 + CH3CON (CH3). C. .

For tion in Zpropanol in the excited state. hTorrish type rcactio~?~.CH3 hv + . COCH. RCH. 2-metllylbenzophenone (A) appears to undergo intramolecular H-abstrac. and it is as reactive towards H-abstraction as benzophenone itself.' -t [Ar.e. The unstable en01 reverts to the 6-hepten-2-one (B) in pentane solution the total photoreaction is: ketone in the ground state. In solvents coiitaining C-H bonds. . and benzyl radical.Type I reaction involves a-cleavage giving rise to an acyl and an alkyl radical.CR -+ 1 11 CH. CH. none with piperylene. fragmentation reaction has to compete with H-abstraction reaction.H-abstraction : Norrisll Type I 1 and Tyye NI rcwc rio~ls Lack of reactivity in some 0-substituted diary1 ketones in spite of ttlcii T.CH. also called Type I1 photoelimination.C 0..COCH. Photodissociation is favoured if a relat- ively stable alkyl radical is ejected. The yields of Tjpe I clsavage :ire usually lower in inert solvents than in vapour phase due to radical recombination by solvent cage effect.C = 0 (TI) + KCH. Dibenzyl ketones fragment very readily in solution to give carbon rnonoxide .x*) state has been found to ke due to the possibility of intran!olecular Wpe 11 reaction occurs in carbonyl compounds which possess y-hydrogen #toms.NR.~ migrates high pressures of biacetyl or 2-butene which quenches the triplet state by to the carbonyl oxygen. . It is generally observed in aliphatic ketones in the vapour state and at high temperatures. -+ rc'~'-] a quantum yield close to unity from the singlet state. energy transfer are not 100% efficient in quenching the photodissociation of acetone in the vapour state.. . Tetramethyl oxetanone undergoes fragmentation Ar. +. The acyl radical is essentially decarbonylated at high temperatures. Sometimes ring closure to form cyclobutanols is favoured. (TI. Suggesting singlet state reaction mechanism for the unquenched fraction. I The reaction can occur from the excited singlet and the triplet state as evidenced from the quenching of reaction in 2-pentanone and 2-hexa- CH. I 0 I~~tramoleculrrr. The reaction proceeds by a shift of a y-hydrogen to ovyzen with H-abstraction &sequent cleavage to an olefine and an enol. =CH2J CHz= CR Y a a H.C \/ C-R I J. Intramolecular interactions have been classified as Norrish Type I1 and Type I11 reactions. Type I cleavage occurs from both singlet and triplet excited state4 since PhotOenolization resembles Type I1 process in that a y-liydro. Piperylene can quench the reaction only partially. . RCHO In effect it is intramolecular H-abstraction followed by P-cleavage and is These compounds are often uscd as photostabilizers in plastic materials. The possibility of such a six-membered transition state does not exist for 2-t-butyl benzophenone. ASPECTS OF ORGANIC AND INORGANIC PHOTOCHEMISTRY 24 1 . - H H 0 / OH I II H2C 0 hv I CH.

+ D + . -. EL + R f 2H+--2e + RH. In such reduction processes.ff?ct. Type 11: When ED > ER and AG < 0. where AG is expressed in Joule and F is the Faraday of electric charge. the reaction should be possible thermodynamically but may not occur because of a high energy of act]- where RH. hydrogen :lb>traction in a triplet state can be expressed in terms of the redox potentials of the two couple: ED and ER D + 2 H + + 2 e + DM.I.) Type 111 reaction involves intramolecular hydrogeLLabstraction together with a-cleavage. Photooxidatiori reactions in absence of ~vnlzcu'at 0.HO. The role of photoexcitation in this case is to p~ovidean steps giving a semiquinone as an intermediate.E. . 4-0. The colour may or may not1 reappear in laboratory could provide a method for photochemical conbcrsion and the dark. The light absorbed by chlorophyh mole- cules pushes an electron energetically uphill.Oz or atmosphere 02 8 2 PHOTBOXIDATIOS A 3 D PIlOTOOXYCENATION or by the photooxidized reductant itself D H f O . The photoreaction goes against the thermochemical gradient and reverses spontaneously in the dark. a potential is dekeloped at suitable electrodes. When the reaction is carried out in an electro- chemical cell. 1 Photooxidation . 1 .9).5).O. The thionine-ferrous system falls in this category. the course of such redox reaction.s like stannoua chloride fall in this category. EL-E~ In terms of these redox potentials the free energy change for the net two electron transfer reaction is given as AG=-2xF(ED --I-. HO. 2 . 1 Photoreduction of Dyes by Two Electron Transfer Processes is the photosynthesis in plants. 8 . In some cases the reaction may be reversed by H. The rsaction is pH and con- serniquinone centration ciependent and the reduct Lnt ir\ consumed during the reaction. two H-atoms (or two electrons and storage of solar energy. oxygen does not participate are better described as photochc~lical:)xi. T h ~ sis known as the photogalvanic c. TWO situations can arise leading to two types of reactions: Type I : When ED < ER and AG > 0. i l i i : t \. + . The photoreduction of rnethylene blue by EDTA or other electron don >. + 2Fe3+ -+ D + 2Fe2+ + 2H+ . Duplicat~ng such a system in the appears to be bleached in light. For example easier route for the reaction. The most impxtant example of such endergonic reactions 8 . thus providing the driving Photoredox reactions are observed for some dyes in which the dye force for the primary processes.'!:. These reactions are not thermo- dynamically feasible in the dark but may occur on photoexcitation of the dye if the free energy differences become favourable (Section 4.ih . DH +DH + D + DHz leucodye Dyes in the rcduced date can act as Lery powerfui reducing agents. is a reducing agent. l'he\e are called pl~otocataiyztclrc~actior~s. HOB -+ H.- Di-l. could be solved (Section 9.> + SOME ASPECTS OF ORGANIC AND INORGANIC PZIOTOCHEMISTRY _ T i Seberal photoisomerization reactions also proceed by i n t r a n ~ o l e c ~ l ~ ~ From thermody namic considerations. D + R H 2 -+ R t D H . if the problem of spatially separating the products two protons) are added t o the dye D. The reaction occurs in two one-electron vation AC*.

Eecrr~r\ tc..- in the general sense of the term. Substrate.. ~~cIi ( h ) forriiiit:~il transfer.r where light is absorbed by it molecule (1) (2) (3) other th In that which reacts and is called a scr~sitizcr. where D S A D ---b S --+ A Di S A- light is absorbed by A designated as the substrate or as ( h ) an ir~clirc'ct process or pllotosei~sitizc.. as an oxidizing agent in the photosensitizedoxidation of organic substrates. (b) transfer of an electron from - The olefins give hydroperoxy compounds and the reaction is called an the lowest filled energy level of D to neutralize this hole and (c) transfer of -'ene' reaction : excited electron from S to the unfilled energy level of A to produce A-.6. For the addition of molecular oxygen a t the double bond $.=C.r.c.pcs o f i n t c ~ . i ~ 2 r t n k ' .tIproc. The reaction is said C. When an addition product AO.ns~t!zedelectron transfer reactlm to occur from the triplet state of the excited ~nolecule. molecular 0. .rs. Three steps can be identified for the final generation of oxidized donor D+ and reduced acceptor A-(Figure 8.sr..r. and ( i i ) Type / I procc>. Pbotoredox reactions can be mediated by an intermediate which is called a sensitizer.2). E ASPECTS OF ORGANIC AND INORGANIC PHOTOCFIEMISTRY 245 i-edriction reactions Ir! whicla 2r-t eiectronically excited donor !no!tc v a rnatic hydrocarbons 'lnd olcfins are good substrates. .~ ..0 ) t~zccl~nni. The Type 11 mechnnisni is In air-saturared or oxygen-saturated sol~ition.Qf singlet oxygen gcnernted by cnergy trnrizfer from excited senniti~cr &Kaursic rnehanisrn. Step andthe final peroxidation step involves acti\e 0 . --C. -+ AO.0 guish il from such photooxidative processev as electron transfer or H-at0111 imechani~m:( 3 ) formation 01' m ~ l o x i : i c .. +- D tzv = IT* Dr t. The sensitizer S finally emerges unreacted.s. l c ~ J i : ~hcl1...--C. The unsaturated i trd~sfers.I n ( D . Two t). 0. i e a r . )ic co~npoundsg i ~ eeiidoperoxldes. energy level schemes for donor D. 2 Sensitized electron transfer reaction obeying spin conservation rule Photooxygenation reactions are con\enien[ly dividcd ~ n t o(i) I : I ' / ~ ( I' Prooclssc. 2 Photooxygenation i~lvolvedas intermediates. ~ r / ~ c ~irzf~c~/rrl/li\t~t.s. is activated i n the interlnediatc A + O . It thus acts as a photocata1:~st I l l ilvio. which finally rencts with 01to form AO. sensitizer S and acceptor A. Figure 8 .c t c s been proposed for D . 2 .s. agent.A r e d Far exaiilple : + (eosinb* F ~ ( c N ) ~ . a peroxide. (a) excitation of an electron in S leaving a (+) hole in the ground state.is i l l --C1==C..participates further subdivided into (D-D) and ( D . i"a = Dor -C. I n (D-0) /~trc~/lrr/ri<i. and the ground statc the reaction is called photooxj~geni~tiot~ to distin- or nl~o~operoxirl~tiorl.-C. The photosensitizad oxidation is illustrated belovd by:. icr:cptsr rnolecsill: (A).s.s in which free radicals and electronically excited inolecules arc 8 .. is formed: the acceptor is activattd in the internlediatc step.D ) n~rchnrlisitl.a!. I \olutlon Pholooxj:genntioiz may take place eiiiizr as ( a ) a dircct proc.-+ [eosin]+ 4 F ~ C N ~ - semioxidized eosin Some examples of photooxidation reaction in inorganic complexes have been discussed in Section 8.in which only electro- nically excited molecules are intermediates.srn.

They are called dim01 absorption or emission. -+ S +lo: 0 2 (??I triplet + S (t4) s i i ~ ~t l e -. Nature and it~lporturiccof singlet oxygen : The electronic energy states only mean that a diffusable reactive intermediate IS generated in the gas of molecular oxygen have been discussed in Section 2 .r by 'oJt4.)* s* -+ o. Therefore. different sets of silica gel. SO.)* +A -t AO. ~ i l c a gel particles and mixed. '0: + A 4 AO. Fo.0. (3Z.( 7882 cm-') + 0. i ~ $ c t oxygeii ok~lccu!er. OC1. oxygenation occurs with .11.8 kJ) above.(l< )I pair state froin p a n of . Dirc~ctexcitation The high specificity of organic photooxygenations can be explained A* -tA 4 AA* S* + A + (3.)" +A -+ AO. merely quenches I*' -+ (A = 476 nm. The only possible calldidate configuration are doubly degenerate 'A. in air-saturated aqueous D. T h ~ could s A. = 15765 cm-1) . is greater than hf oximately.reaction consists of lines at 480 and 634 nm. )OI(E ASPECTS OF ORGANIC AND INORGANIC PHOTOCHEMISTRY 2d7 iplet excitation of the sens~tizerand thus inhibits other photochemical All these types of reactions can dcchre~ther by direct excitation or by nts. singlct + S(t4) slr~glct -L SOs(t+?C) singlct radiation absorbed by sensitizer only. These higher energy states of 0.. + 021Ag]pair state (A = 634 nm. C.120 cm-1) (chenilumioc\runc~)eiiiittad from thc reaction mixture is doe to emissio!' '[O.21 kJ) and appears to ?xan active generated by energy transfer process: {38 kcal or 158.( ~ f13. When illuminated in presence of 0xygt. generated by the simultaneous transitions in a pair of oxygen molecules The Kautsky mechanism was not accepted for a long time because not with a single photon.3 kcal or 93. At ordinary temper~:ures. reacts in its singlet state. red do'" O a 'A. But in some f'avourable substrates. which emit at 1270 and 760 nm. An ~ntermediate complex or moloxid: of is a triplet 3Z. molecules ir~teresti n this mechanism was revived when in 1964. oxygenation of a large number of substrates was the same when the and the energy of the 476 nm state is just the sum of the energies of oxidation was carried out in the dark using M. emission spectrum of chemiluminescence from + HaO.c!l i n tlre cuor.>te and his collaborators demonstrated that the product distribution in 2 0 s ('A. The sensitizer w. 7 while the potential phase which can live long enough to ox~dise the substrate adsorbed on energy curves have been given in Figure 2. ~ have the product in the singlet stdte which may be its ground state: The sensitizer and the substrate were adsorbed on separate sets of .4' three major requirements for highly probable reaction: (1) the reaction st be exothermic.) (A = 1260 nm. -+ (so. The ground state of 0. +S molecule S is not very probable since the complex SO.)* e reaction of ground state 0.) with ground state singlet organic (AO. The product in the triplet state irliplies it to be in a higher excited state. 0.l. Thus much was known about the reactivity oflO: molecule at that time The 634 nm state has the energy of two =A.:. + (AO.) 4. These lines are observed in absorption spectrum of liquid oxygen which has a blue appearance. will be generated in the triplet state from spin considerations: (b) Kautsky mechanism A* + 0.('A. this reaction should be strongly endothermic and hence not The singlet oxygen mechanism was first proposed by Kautsky i!i 1330 very probable. = . this means that 0.:.e of r. (22. (?t.~. A* $0.and the next higher energy states of the same electronic Schenck would be too bulky to diffuse.003 cm-')- .i.~c~c~lra~~ist?z actants (rille for conservation of s p ~ n and ) (3) the symmetry of the system (a) Schenck mechanism ust not change during the reaction (rule for conservation of parity).av photosensitized pathways : *~+i* quantum yields if the concentration of 0. On the other hand. = 7882 cm-') + '[O. AO. respectively. (2) the total spin of the products must equal that of the D-0~. l -. must enter the reaction in an ited state.ts not changed by the reaction. we to explain sensitized oxidation of substrates when adsorbed on S I ~ I Lgel.lA. . +A (SO.D r?lcchnnism utions [O. -+ A f1O: S* + 0. tr~plet lot+ A -+ AO."' In i n i t photochemical rcrition ini~turas. Besides these two lines. 21. i f 0. are explained to be A +'Of -.O.] e 6 x 10-4 M. high yield of oxygenated subscrate was obtained. S. NaOCl rnixtllre+ '' 'A8 and states : tile oridnr!r.praili~. The decoinpositioir of liydrogen peroxide in prerenci: sodium hypochlorite is keoivn to gsnciate rbiglet O X ~ ~ P I IA.

--. 0 and multiplicity 2s 1 = 5. reactioris and systems in ~vhlch siilgiet ouygeli is IIOR. energy states.12). substrate in the singlet sfate 'A and a ground state oxygen 30. not involve energy transfer but is entirely due to enhanced intelsystem n:sntal chen~istry and existence of life it5elf on our planet earth. . I lie sate constants i'or the 0. 3 Quenching of triplet state of a substrate. 2 + 3S + 0. The '2. Energy transfer between S*4302 . c X T .. No change in as CCI. A collision complex between of two 'Z. ('G.ri>n. Thus a total of The intensity of'these collision induced transitions is borrowed frbln the nine states are obtained and the singlet state is only one of these nine dipole-allowed transitioh B3Z. em^ ASPECTS OF ORGANIC AND INORGANIC PHOTOCHEMISTRY 249 I At still higher energy.) is the likely product. ifil~~gi o r . r~ The quenching of triplet state can occur by energy transfer through collision and quickly deactivate. = I. crossing. S = 2. ' A . 1.~!bio~i-controlled. been suggested to be the re. 3.6. state is \cry sensitiv:. 1. Singlet oxygen is clearly invol~edin numerous dye-senr~i~ze! photooxygeilation ~. state llas the proper s>.1 C. These cooperative double molecule al.~ l ~ f ~ ~ c r .i. Kunge system (Figure 2..ce Figure 8 .-quenching of exciteil \inglct and triplet s t a b are g i ~ e nin Table 8 .ctrons takes place during the process '3. states. of aro~natic hyJ~. energy ET lies above the singlet states of oxygen molecule. (12. the total spin orientation of th: el. E isl-TI) cm-l constant constant Otherwise energy transfer is the favoured ~iiechanismbeing nearly 1000 times Lq x 1010 1 mol-1 s-1 kq x 109 1 moi-A s-' fastar than the intersystem crossing rate. is viil C'I! exchange mechanism to generate singlet oxygen if the sensitizer triplet state dependent and has a Iligh \. In vidter thc Iif'etinie i h 2 :.) = 19.) = 45 min.1 Antliracenz 1. F . (Figure 8. No Rnie constants for 0 .= + S1 = 1. and in the quenclling of thi: excited singlet and triplet states of mo1eculi. ('A.) 2 O2 ('Z:) ( v L + 0. ha. . which may proceed via a CT-complex state (Section 6. the oxygen-quenching of singlet states does single molecule transitions in 0.trbo~ls. i ~ o ~ hini l ~conic:!ed ~ [iddition rcactions to d o ~ ~ b lbonds. )] pair statc " in the triplet state. i i !.state of 0.-') quintet. by SO2 generating 1 0 % by exchange mechanism. h radiative lifetime than ]A. Ndphthalcne 10.2).to act as a i l i c .eactionsol' olefins. Kinetics of photoperoxidation reaction.~rbo~l\ both in holutio11 and in vapour phase is in gr:ner.s.drogencontaining solvent .: i('Zi In condensed syhterns the actual lifetimes :ire: ) 7~ . photody~laniicaction. 3S. .i!. and if ET 159 kJ mol-I. ~ ~bj' c ~ ~ ~The ~ r ~oxygen ~ ~ ~ quenching offluoresce~. .l~tlig consta~ltsaFe one-ninth of !he singlet .3) : more. 0. absorntion at 381 nm correspond\ to summation because of spin statistical factors.8 2.0 given in Figure 8.lc.500 2.000 1. triplet and singlet states according to Wigner's rule: S. have profound influence in en~. (]A.il ilili.lcti\e state of singlet oxygen. dienes and aromatic hydroc. ( I ~ i ~ ~ ~ r cu~f l' r.) acts as dienophile and adds to give the endoperoxide in concerted addition reaction similar to Diels-Alder 7 1 . The energy level schemes for /- some suitable sensitizers of photooxygenation in relation to that of Ozare Ijenzene 8700 16. There are reasons to U F ~ L ' \ that I si~lgletoxygen may also be involved in cliemilunli!iescent phenomena. (3Z) -+ S O2 (IZ) or O2 (lh) > If ET 159 kJ/mol-l (13000 cm-l).0 12. 26242 en.. 13.q u c ~ i ~ h i nof g excitcd sinslet and triplet g a t e rnolecuks.llue i n noti-l~). phetocarcinogeni~~it!' and perhaps cveil in n~ctalcatalvzed oxygcnation reactions. ('Z:) may be produced which decays .will be 13120 cni-I) .lnmcis\. energy transfer can occur if E ~ < 9 kJ 2 mol-l (8000 cm-I).4. 0.d In aromatic hydrocarbons.oc. TIie '2.believed to be directly or ~ndirectly involved is intiecd remiirkable.rrluLL s. In such cases Sil~gletquenching Triplet quenching quenching involves enhanced intersystem crossing to the ground state.+ '[O. tri]. I-rom these co~lsidel.6 2. to Thr: lifetime of 'A. But the complex between 3A and 802can produce i (A = 381 nni. commonly known as ScIlumnai>.l ~ ~luzrt~. In the sensitized photooxy- / fienation by Type IIb mechanism the 0. has a n i ~ ~ cshorter and r ('1. 2 < rapidly to 1A. ~ :W2.\ 10 ' ' \ .S . i('2:) c 10--Io s and r (la.~~::-. e Thc range of phenomena.

0. In the 'ene' reaction.002. k1 'SI 4 ISo + hvf Fluorescence kz 'SI ----t 'So Internal conversion k3 IS.of the oxygen molecule to one of the carbon atoms of the double bond (e. +A AO. 10.+CJ and (iii) migration of the allyl hydrogen atom to the terminus of the peroxy group./k. Thq urn yield of AO.)-lvs [A]-l at @nstant [O. +AOz.---+ k4 3S1$ 30. A = substrate).g. which in turn react faster than IS.=.. Decay of singlet oxygen -. bromobenzene and CS. formation.). C.0.]. ISl Absorption (.'0. 0. values are Rose befig31 Oxygen Chlorophy ll Anthraccne rho sensitive to the nature of solvent.-quenching of singlet state dialk~l-substitutedones. when the photoreaction is studied as a function of substrata *centration. It can obtained as slope/intercept ratio from a plot of (+A~. The following reaction sequence is found to occur in aromatic is shifted to the allyl position with respect to the starting material hydrocarbons in presence of suitable sensitizers which may be a dye or according to the scheme proposed by Schenck. This involves (i) attach- another or same aromatic hydrocarbon: ment. + 30. (ii) formation of singlet Mgen $10.12. . k5 3s1 ---f SO Reverse intersystem crossing SS.---+ 'So k6 t.g.*many cases. (ii) shift of the double bond to allyl position (e. so ). D. Energy transfer to generate '0% OOH Tetramethyl ethylene (TME) '0. Mechanism of 'ene' reaction.is given by the product of quantum of (i) formation of sensitizer triplet state #T. (S = sensitizer.42. Photooxygenation . stereoselective introduction of a hydroperoxy group occurs k &h makes this reaction very valuable in synthetic organic chemistry. the double bond adducts. 3'- -(so I. P is known as the substrate reactivity parameter. K7 -4 so.. tetraalkyl-substituted double bonds react at a faster rate than do trialkyl-substituted double bonds. The values for photoperoxidation varj with substrates over five orders of magnitude : P = 55 M for relatively unreactive cyclohexene and I v s * -.+ 30. --+ SS1 Intersystem crossing general. in relation to that of 0. FUNDAMENTALS OF PHOTOCHEMISTR~ MPECTS OF ORGANIC AND INORGANIC PHOTOCHEMISTRY 25 1 direct oxygenation S = A. 4 Energy level schemes for some suitable sensitizers of photooxygenation 0. . to 'So + hv ---t 1. For autoperoxidation of anthra- mne in solvents benzene. 3 x M for reactive dimethylanthracene and rubrene. respecti\e valces are Figure 8 .and (iii) of oxygenation step +R l(be ratio k.

%-unsaturated compounds are known to dimerize when Qpcised to suitable radiation. With electron rich olefins 1.bond p 00"l OOH S-K' I 0-0 - R-S-K' 2R-SO-R sultoxide The energy required for bond cleavage is about 146.2-1. dioxetanes which cleave to give carbonyi fragmentb: sulfones During the process of thermal decomposition.4 addition. This explains the absence of photoperoxidatron In phenanthrene and naph- thalene where not much resonance energy is gained or lost. If the gain is large enough. SIl It is thought t o proceed by way of excinzer formation (Section . (b) 1.2 cycloaddition forms retatrvely unstable /IV:O.2 addition. one of the carbonyls is Produced in the excited state.1 Photodimerization Photodimerization involves 1: 1 adduct formation between an excited and a ground state molecule.4-1.SO. 4 2 CtfJ. singlet oxygen may be generated in the decomposition process. The lalter mode is favdured ~f the resonance energy for stabili- =tion of the hydrocarbon upon regeneration is small. 8 3 CYCLOADDITION REACTIONS 43. Photodimerization of anthracene is one of the well documented *tions. aromatic hydrocarbons.3 kJ (35 kcall rnol-').. FUNDAMENTALS OF PHOTOCHBMIST~ we ASPECTS OF ORGANIC AND INORGANIC I'HOSOCHEMIS-L'RY 253 252 Few other reltctior~sare: The endoperoxides may decompose in two ways: (I) evolution of ecular oxygen and regeneration of original substrate and (2) by the age of -0-0.4 addition or 1.CH. often emitting to produce ckremilumine~ence. Crnjugated dienes.2-1. Olefinic compounds./~ -. Photodimerization of olefinic compounds Occur by either (a) 1.

4-1. This suggests that since rotation around the central bond in the excited state is a ~ O L Vprocess it will not effectively compete with dimerizat ion.linly 1. x " ) state which m a j be a singlet or a triplet.3). 2-1. 6. Irradiation of butadiene > in the presence of triplet sensitizers with El. But for molecules whose triplet energy lies between 226 kJ and 251 kJ compound (3) is formed in large amounts.substituted anthracenes can be dimerized Four isomers are possible rys-syn. Pairrrlo-Buchi reaction. (n.2 Oxetane Forniation in a nuntber of ways. 5 ) . ET of cis-butadiene is 226 kJ. syn-anti. ( x . The reaction is not quenched by oxjgen.z") i n character and an electrophilic centre is created on carbonyl oxygen atom on photoexcitation (Section 8. The direct and photosensitizeit reactio~ls are likely to give different products because IS(' of the inefficiency in S.251 kJ leads to dimerization 8.1). The photodimerization of a. 4 addition reaction form~ng dianthracene as !lie single product coumarin ( A ) syn from S. 10 compounds d o not dimerize because of steric hindrance (Table.3. )1m ASPECTS OF ORGANIC AND INORGANIC PHOTOCHEMISTRY 255 6 . For example. 9-. The reaction occur from the triplet state as confirmed by acetone sensitized photodimerization of thymine. It is a 1. z*) state. P-unsaturated carbony1 com~oundsoccurs from either an 01. The reaction proceeds from the IS. coumarins photodimerize to give two main products as shown below: . x * ) state in absences of f t a t e In presence of sensit~zer benzophenonc Photodimerization of thymin to butane type dimers i n one of the important causes of U'4 radiation damage to genetic material D N A in its native double helix form. anti-syn and anti-anti but 9. n * ) (tl) ant1 fiom T1 ( n . In polyenes. 2 addition: The cycloaddition reactions to gibe oxetanei readily occurs when T1state is (n. These dimers can be monomerized when irradiated by short wavelength radiations which are absorbed by the dinler only. -+ TI transition. m. dimerization occurs horn the triplet states. x * ) or a ( x .

.lar orbitals (HOMO) are of direct interest immediately helps to make predictions regarding the feasibility of the reaction. C! t i 4 a18s (Sec. by the free . the motion is called disroruror~. the orbital lobes must rotate either inwards or In these cycloaddition reactions which may be intermolecular. ~ i i i states of the two reacfents: ) =c >c=L< dlmer~zat~on on cni. The reverse occurs ()Pan to rotate inwards and the other outwards. $ectron (It. From the analysis of the orbital and state symmetries of the initial and final state.. - ' 7. The 4-C atoms give I I ~ shown i n Figure 8. E) model.. it may not occur even if thermodynamically allowed. the of HOMO is as described by JI. products.1 Conrotatory and Disrotatory blotion the HOMO of interest is 44. Consider the cyclization reaction: butadiene $ cyclobutene . If a reaction is not allowed by the rule for the conservation of 'qmmetry describing the phenomenon of ring closure In the ground state. On the other hand. such %Car to move outwards or inwards. on by bringing the like phases of the lobes to overlap facilitating rmation i n the thermal reaction. . 2.n olefin is dependent u p o n die relatavc energies .4. in the excited 8.5 MO's of butadienee. If both the lobes move in the same directions such that one intramolecular.^-*) -+ -- (11) . . a r-bond is converted into a o-bond.5. orbital occupancy diagram and electronic state diagram. If the two lobes move in opposite directions such that both movement of electrons and atoms but no atoms are gained or lost. Now the disrotatory nrotiorl creates a ing situation predicting ring closure in the phoroche~?~ical reaction. I - --+ oxetane formailon . The rule is based on the principle that the symmetry of the reactants must be conserved in the Figure 8. transfer to olefiii I . The closure or opening involves t h e *"rOtarory.\f ihe i t ? . 0' &wards.) to form endoperoxides and photochemical Diels-Alders reaction MO' s of buladiene diagram can be rationalized by the Woodward-Hofman Rule.1) N o energy transfer: TI".10. w 1 Oxetane formation 'I E xciied stale > i-' Ground state SO A 8.. transformations have been called electrocyclic reactions and may occur liom the diagram it is evident that conrotatory motion will cause a bonding thermally or photoche. For ring closure symmetry. (Figure 8 5). a state correlation diagram can be set up which ' The highest occupied rnolecz. b e n10lec:i:~lr orhitals o!' butadictu: call hc: p ~ r i ciiled t. (IA.nically as governed by symmetry considerations.4 WOODWARD-HOFFMAN RULE OF ELECTROCYCLIC REACTIONS The photochemical dimerization of unsaturated hydrocarbons such as olefins and aromatics. Ffl ASPECTS OF ORGANIC AWD INORG*NIC PUOTOCIIEMISTRY 2 57 The eH1~1er1cyof cyclo ld~jition o i an arotnatic c~irbot~yE con-tpc-~. the motion is called when ring opening taker place. cycloaddition reactions including the addition of E lectrmic state 0. kween C-atoms 1 and 4.

TABLE 8 .5. 8 . 4 . AIII.<I~II~ disrotatory mode.[ the systenls may be attempted. On the other hand. The 4 orbitals of cyclobutene are o. i n the 'Tsbie 8 . and the new configuration is indistinguishable from 'l" original.6). a* and x. In the case of conrotatory mode. 1 Reactant and Product Oribital Symmetry Correlation In the reverse transformation. On 110' rotation along this axis. 3 Cyclobutene + Butadiene l o I"*/" * I 8 1 / h l h l C Cz-axis symmetry conrotatory mode la ib i b l a I*Ib la lb lo 1 Mirror symmetry disrotatory mode 1 / 1 1 1 1 1 1 ( a1 at' a' a" a1 aU a' a" Thus for the conrotatory mode.258 FUNDAMENTALS OF P H O T O C I I E ~ I I S T ~ ~ SOME ASPECTS OF ORGANIC AND INORGANIC PHOTOCHEMISTRY If we analyze the case of hexatriene to cyclohexadiene conversion. and a* and x* with 4. axis of rotation. in the case of disrotatorjr mod'' the elements of symmetry are described with respect to a mirror plane. The thermal reaction should be disrotat. to H .X) of . Ths natu" Cyclobutene butadlene Conrotatory mode Cyclobutene =butadlens D~srotatorymode GIeach l. and For the +. X * symmetry operatLon ow (Figure 8. and butadiene illustrated in Figure 8. tory modes follow different correlation paths because they preserve differell' b t a* 2 symmetry elements as illustrated in Figure 8.. diene transformation for (a) conrotatory and (b) disrotatory modes. The conrotatory and disrota. and a generalizat~o~ . ]sac symmetry and antisymmetry of an orbital \vith respect to a mirror P of reflcciion is dcnotcil by a' w d a'' respectii ely (Section 2 9). The 4 orbitals of the product are the familiar MO's of Figure 8 .ycl~hiltenewith rospcci to these two operations is she"''' Figure 8.7. the symmetry is preserved with resPEi to C . Figure 8 .8) the four orbitals of cyclobutene. the ring opening of cyclobutene to gi\e A n s of rotat~on M~rrerplane butadiene. and Jr. Each of the first set of orbitals passes over into the second set and it is instructive to examine how the sets of orbitals correlate during the transformation.and 6.8 ~eactant-product orbital correlation diagram for c y ~ l o b u t e n e ~ b u t ~ . the conversion involves net transformation of a o-bonding oibital conrotatory rrode d~srotatorymode symmetry operatton C to x-bonding orbital. u and n correlate with Jr. a and x* of cyclobutene have the same B~anfj~tir~ symmetry as I ). and the photochemical reaction conrotatory.. . 6 MO's of' cyclobutene and Jra. 4 for cyclobutene and butadiene. ttic situation is just the reverse.!. of butadiene and a* and n as Jr. 7 Symmetry operations for conrotatory and disrotatory modes of cyclobutene + butadiene transformation. HI goes to H" and H.1 a'' antisymmetric as b.!)OI. Below are arranged (Figure 8. The butadiene belongs (4n) x system and hexadiene to (4n + 2) x system. An orbital symmetric with respect to rotation is called .

In the reverse reaction. and similarly for a' = ( + I ) and b'= (-1). (b) Conrotatory mode.9).4. For other energy states from the orr responding occupancy configurations for conrotatory mode we have: Conrotaray mode ( b) F h 8. which is totally symmetric and belongs to the symmetric species designated by -the symbol A. ground state cyclobutene transforms to doubly excited state 4.in conrotatory mode which is the mode for thermal reaction. But the flnt excited state of * i t h t cyclobutene butadiene transformation is energetically allowed . both in the forward and reverse directions.4. The ground state electronic configuratim of cyclobutene is 02x2. the ground state of butadiene correlates with the doubly excited state of cyclobutene u2 z * ~ . BY Mich is the @hC configuration and correlates with a higher excited referring back to the orbital symmetry correlation diagram. 9 b). b i e r .. In the disrotatory mode.4. orbital of butadiene in conrotatory mode and 4.4.Both the transformations are highly unfavourable for photochemical reaction.Nth the lowest state or B symmetry in butadiene is through an energy of symmetry A of cyclobutene can correlate with the ground state of . The conclusion that is drawn from such correlation diagram is butadiene of symmetry A (Figure 8 .2). we note that in "ate in cyclobutene. the ground state .set up (Figure 8. relates with orbital of butadiene in conrotatory mode and with orbital in the disrotatory mode. These states for reactants and products can be arranged according to their Wmctry B of butadiene. It is thus seen that the u-orbital of cyclobutene tor- +.9 . Therefore.9). This eransforms to the ground state of butadiene 4.8) the ground state composed of 0 and x orbitals* way whereby the first excited state of cyclobutene can be correlated correlates with and q2 orbitals of butadiene. On applying the noncrossing rule we h d that the conrotatory mode (Figure 8. Similarly. Wobutene (aa.2 State Symmetry Correlation The symmetry of the electronic energy states can be derived from group - theoretical considerations (Section 2. Therefore. This is not the lowest state of B symmetry state of relative energies and a state correlation diagram.orbital in disrotatory mode. State correlation diagram for cyclobutene # butadiene transfoma- tion. +)of symmetry B must correlate with (II. D~srotatwymode la) 8.260 FUNDAMENTALS OF PHOTOCHEMISTRY ~ o M E ASPECIS OF ORGANIC AND INORGANIC PHOTOCHEMISTRY 26 1 those of butadiene in order of their relative energies with levels of the same symmetries joined with due considerations of the two reactant-product symmetry correlation rules : (a) it is not possible to jump an MO of the same symmetry and (b) the orbitals of the same symmetry do not cross (noncrossing rule) (Section 4. the ground state of the cyclobutene is derived as: ZP = (+1)' (-1)"1.of butadiene. putting the eigenvalue for the symmetric functions : a (+1) and for b = (. x-orbital of cyclobutane correlates with 4. (a) Disrotatory mode. the reaction is allowed thermally.1).

If SS and SA configurations of the reactants are represented as x: and x. ~ - or ground state reaction. + n bonds In electrocyclic reactions in which interconversion of one x-bond +one a-bond bv I I of rearfan t s I occurs. From the state correlation diagram (Figure 8. Such correlation diagrams for higher dienes lead us to the generalization: +I+ . Now the barrier appears in the thermal 8'8 8:s $8 8 . however for m = 4n 2 system the process 818 818 818 is thermally disrotatory i f it proceeds at all and photochemically conrotatory. are the -n of x-electrons in the two reacting symmetry and antisymmetry are represented by S and A respectively and bners. Two planes of symmetry are thereby set up: 0. . the process will be allowed photo- worked out. To respect to these planes of symmetry for the two reacting partners can be Bneralize the selection rules for the above reactions in which two %-bondlead to two o-bonds (2%+ 2u). By a similar reasoning a state correlation diagram for disrotatory mode can be drawn up (Figure 8. On the other hand. o*-a.-per.and AS and AA as x.9a). 3. then an orbital correlation diagram can be Set up: a and b again stand for symnletric and antisymmetric functions ~ t respect h to the molecular plane and the levels are arranged according to their relative energies (Figure 8.11).5). The same can be done for the product cyclobutane in which these =-bonds are converted into a-bonds (Figure 8. The + + c ~ m i c a l l yfw m. whereas the excited state of the reactant correlates smoothly with that of the product.0" pendicular to the molecular plane bisecting the bond axes: ov-parallelto %' CV a . + cr. 0h . -I+ .+ and x.12 b) it is predicted that the Found state thermal reaction is not allowed because of large energy barrier Imposed by symmetry restrictions. etc.12 a). CQrrelate smoothly and hence the reaction is symmetry allo~ved pphoro- ~hemir-sll~.. (4) (a2) (C3) '04 1 Figure 8.). 2.. if the number of x-electrons m = 4n (where n is an integer. o. m. 1 . h Bonding Ant~bonding Bonding WaKly antIbonding the molecular plane lying in between the two molecules (Figure 8.. = 411 2.1 .10 Elements of symmetry in concerted cycloaddition reaction: 2-ethylene e cyclobutane.4. and the four configurations of the product as o. + i*hkrc m. planes thermally but is dlficult photochemically in conrotatory mode.10). the eltctrocyclic reaction is thermally conrotatory and photochemically + disrotatory if it proceeds at all. and a.The t-ansitipn state pos~ulated for this photochemical The symmetry properties of x-MO's of ethylene. respectively. o.. The proper geometry for the concerted action would be for the two ethylene molecules to orient a one over the other.11 Symmetry properties of MO's for ethylene and cyclobutane: T-bonds of reactants and a-bonds of products. SOME ASPECTS OF ORGANIC AND INORGANIC PHOTOCHEMISTRY 263 262 FUNDAMENTALS OF PHOTOCHEMISTR~ double symbols represent symmetry with respect to uh and o. The 'reaction will occur photochemically. and m. the 2x 2x cycloaddition. 8. 0. formed by the in-pnase Eactiorr is a dimer formed from one ground state molecule and anotner and out-phase conlbination of two p orbitals in each molecule with excited s@te molecuie and has been termed as an excimer (Section 6. the excited states Figure 8. The simplest case is the dimerization of ethylene molecules to + give cyclobutane.. = 4n and thecmashemically for r n ~ m.3 Cycloaddition Reactions The concept of the conservation of orbital symmetry can be extended to intermolecular cycloaddition reactions which occur in a concerted manner.

a reaction must provide sufficient excitation energy and at least one species capable of being transferred to an electronically excited state. the higher excited sfate ( l A o . But the transition state for lA.) must lead to the product in an excited singlet state 8. Thus a system of reaction coordinates favouring production of excited states rather than the ground states is essential. Such transfer is possible: in large hydrocarnon molecules becaurc the geometries of the reactant ions and thek excited *teSf are not very different. .. and not by ground state tr~pletguygen.0. When the electron is transferred from the anion to the antibonding orbital of the cation with proper spin configuration.5 CHEMILUMINESCENCE Chemiluminescence is defined as the production of light by chemical reactions.02t1C. 4: (bf (8. Chemiluminescence is also generated by a radical-ion recombination mechanism as observed when polycyclic aromatic hydrocarbons in solution a1.AH ranging between 170 . Hence only rather fast exergonic reactions. . electron transfer or oxidation reactions.. state can react with the substrate to give the products in the p u n d state.21 +cL deperlds on the chemical efficiency 4: of the formation of excited product molecules and on the quantum yield of emission df from thts excited molecule. ME ASPECTS OF ORGANIC AND INORGANIC PHOTOCHEMISTRY I" i These considerations help to understand why oxygenation of olefins isnd aromatic hydrocarbons occurs through excited singlet oxygens. .2.e electrolyzed (Figure 8. .e. The quantum efficiency of a chemiluminescent reaction is defined as +CL number of photons emitted = molecules of A (or B) consunled . a shglet excited state of the aompound is formed wh~cn can be deactivated by emission. i. can be chemiluminescent in the visible range of the spectrum..) can only correlate with a n excited state. To be chemiluminescent. In the plloto- poxidation reactions both the spin conservation rule and symmetry conservation rule are important (Section 8.13). The lowest singlet state of O. These are in general.(aZ.) + 3(A0. Furlhermore.2). the lA.300 k J mol-l. . The anion contains an extra electron in the aatibonding orbital whereas the cation is electron deficient in its h~ghest bonding x-orbital.

o. and the oxidation is very sensitive to metal catalysts and pH of the emission spectrum is similar to fluorescence of 9. The reaction produces a red glow with emission bands at am.1 .NO^ O=C-0 1 1 dioxetanedione recombination.O. I NO/. 9. 10-d~phenyl. 762 nm and 633 nm which have been identified as emission from . The luminol is oxidized by H. This reaction has been extensively studied by Kasha and his borators. FUNDAMENTALS OF PHOTOCHEMISTRY ASPECTS OF ORGANIC AND INORGANIC PHO~UCHEMISTRY 26j In presence of a suitable fluorescer. $eth0xy anthracene although it is not excited directly. Ac!d . 9 ~ ) . 1 3 Chemilurninescence from excited state generated by radical-ion 4 gf. In such NO. the concerted bond cleavage of dioxetane. 2 dioxetane 36 31 Figure 8 . + H z 0 2 -+ O=C-0 The primary requirement of a chemiluminescent reaction is that it I I Fluorescer should be energy-suficient. the emission from the fluorescer is ?* . If the energy of the reaction is not enough to 0/C\o-<>No2 4 promote the product to first excited singlet state. should yield one carboxyl moiety in the excited state *Vcen alkaline solution of H20.-+ 3Ar* + Ar Fluorescer hv + 3Ar* + 3Ar* lAr* + Ar When generated electrochemically the emission is termed 'electro- chemiluminescence' (Section 5 . of the endoperoxide to (1) and (3) is the excitation producing step in On the basis of Woodward-Hoffman rule of conservation of orbital w-atalyzed cleavage and (2) is activated by energy transfer.(hypochlo- ion). J Ar+ + Ar. a 4-membered ring 'mation of lo2by elimination reaction is a very minor reaction step. The decomposi- Decomposition of oxetanes is still another chemiluminescent reaction. and either C1. Chemiluminescence has been observed in oxidation reactions of hydrazides of which luminol (3-amino cyclicphthalhydrazide) is an important example. 6 0 LC/ . The symmetry. wc*o d PCH3 C s c I .%4& H Eu-chelate &HJ)8-~ -C< -+ emission of red Eu3+ line at 613 nm. the system is said to be Dioxitanedione-Fluorescer Complex energy-deficient and molecules in the triplet states may be formed. 4.4- solution.lO-diphenyl-1./ I cases triplet-triplet annhilation of initially generated triplets may populate oxalic ester 1 2 O = C = O t Fluorescer* an excited singlet state. 4 d~methoxyanthracene 0 - @ endoperox I de + In luminol chemiluminescence and that of other cyclic hydrazides the corresponding dicarboxylate ion is the emitter. An inorganic chemiluminescent reaction system involves the reaction * peroxide. The general reaction sequence is 6 OCH. gas or OCl.c=o \H I + c $4 OCH3 OCHJ OCH. I I CH3 0-0 $ b e t h y l 1.

e-. nescence to suitable acceptor is given in Figure 8. i. h) x-d states.2. 0 T 0 Metastable molecular .generating singlet oxygen and . This can be considered 'btransfer of an electron from the metal (M) to the ligand (L) and hence k~termed CTML type. E r lo4 1 mol-l cm-l. The metal ions oxygen levels acceptor molecules Wturb them only slightly but can drastically afferx the photophysicnl Sensitized emission from suitable acceptor in cherniluminescence Processes. These states arise from localized transition within the %nd energy levels. The electronic energy levels of molecular oxygen and excited nergy manifold or delocalized. Such states are expected to arise from a promotion of electronic charge from ligand x-system to the higher orbitals of the metal (e-type for Oh symmetry). x * ) state should lie at relatively low energy for easily oxidizable complex. tals are available (Section 2.OCI. originating from them. Because of the rte forbidden nature. and 'double-molecule' single quantum transis citation and of overall symmetry of the complex which may vary tion form 2[lAg] (Section 8.In Fig. x* states.1-150 4 mol-l cm-l. molar extinction values are low. (nonbonding) to e.Y9] Eosin net bonding in the complex and causes a lengthening of the metal 0 C -B gand bonds. These are not very well established. The resulting increase in antibondingelectron density decreases 1 ['A +'. Figme 8. the charge transfer from the ligand to the metal may also occur. If suitable acceptors are present. lZg] and + Oh to Cs. nce is determined by A. x* respectively.e. Since such transfers leave the metal ion temporarily in an oxidized state such states are related to the redox potentials of the bmplex.11). They lie at relatively high energies. Further splitting of the 1 may arise due to interelectronic repulsion terms. ZOO00 - fi) d-x* states. The (d. The emission from ['A. The A is a ion of ligand field strengths. The energy concentration. Thus the change of central metal ion will considerably affect the position of the (d.2 are given energy level scheme for Oh (octahedral) metry for a-bonding ligands. ASPECTS OF ORGANIC AND INORGANIC PHOTOCHEMISTRY 269 singlet oxygen lA. x*) states.14. d-d states or ligand-jield states. For large organic molecules because of the possibility of different orbital types . tne excited s~ngletand dimeric ener ltals are also available. 8 . For R-bonding ligands a set of x . The sensitized chemiluminescence of the acceptor is d within the metal ion energy manifold or within the organic observed. A set of metal orbitals anda set of ligand 211ZJ double-molecule state is also observed at 478 nm and 366 nQ. These are termed as follows: singlet molecular oxygen pairs available for energy transfer in chemilumi. 2. Basically four different types of low lying gY states can be described depending on whether the excitation is states of oxygen.14 reaction between HBOB+. These states are 0 C 21' X+] Anthrecene according to group symmetry nomenclature. They arise from promotion of an scence of the acceptor molecule shows a square dependence on the peroxide ron frnm t. the ligand field parameter.2A).. chemically generated during the reaction. Electrunlc levels ($) x. (ant~bondingorbital) for octahedral etry. type transitions. These arise from excitation of a metal electron to a pfiantibonding orbital located on the ligand system. The chemiIumine. and lZ. can transfer energy to them. an exictation confined essentially to the inetal ion. singlet oxygen pair states. 3 ~ . CTLM 2. the position of the metal ion in the odic table and the oxidation state of the ion.ha* coupling interactions to give singIet and tripiei states. The reverse process. 6 TRANSITION METAL COMPLEXES Each of thege promotional types of energy states can further split by The photochemistry of transition metal complexes is more varied . They have charge transfer character and high molar extinction.

+ S. The efficiency t$f is low and is related to the spacing and coupling of lowest excited vibronic levels with the ground state vibronic levels. The classical examples are emission from rare-earths. are temperature 8. dDcomplexes and for most d6 complexesisconsistent with the existence in these complexes of low lying d-d states. Rh3+..). (~hen)s] C1. These are d d emitters and spin-forbidden phosphorescence generally predominates. Phosphorescence is charac. These levels can also be modified by solvent effects.270 FUNDAMENTALS OF PHOTOCHEMISTR~ heavier elements the total angular momentum quantum number J becomes a 'good' quantum number (Section 2. exchanging ligands. The relative ordering of energy levels can be altered by replacing metal ions. from CrSt complexes. in solid [RhCI. ] and (c) s(d-d) state In sol~d (b) 3(d.6 vibrational modes a 3n . (I) absorption. x*) state in [Rh (phen).5). (2) Ftersystem crossing.15. Emission from transition metal complexes obey Kasha's rule and originate from the lowest excited state which are (i) 3(x. (4) photo- terized by very small Stoke's shift and resolved vibrational structure at reactlon from 2E. n * ) state in [ R ~ ( b p y ) ~CI. Gd3+. x*) state in [Ru (bpy)d Cl. low temperature in glassy solutions and arises from =Eg4 4A.16. d7. and (iii) 3(d-d) state. Fluorescence is generally broad.g transitions (5) photoreaction from 4T2. and 7. n*j state in [Rh(phen)3](C10q). ( 3 ) VI brational relaxation. [Rh(Cl)n (phen)J CI.6. Sometimes weak fluorescence is also obsrved. For SmS+. Their characteristics differ in details and are given in Figure 8. Emission from (a) s ( r . Spin-orbital coupling interaction energy can vary from 500 cm-I (CoS+) to 4000 cm-I (Irq). in ethanol-methanol glass.1 Photophysical Processes Very few inorganic complexes fluoresce. structured and exhibits large Stoke's shift which indicate Metal-ligand band length - Figure 8. Eu3+. or nonradiative return to ground state. Thus spin-orbit coupling is not the only deciding factor for the loss of luminescence The absence of emission for dl. To adequately represent the 3n . dB. geometrical distortion of the excited state. The levels are populated by intramolecular energy transfer in the complex when radiation is abhorbed by the ligand. In these complexes nonradiative internal conversion k ~ cis relatively more efficient than nonradiative intersystem crossing. . Amongst the transition metal complexes. If the emitting state of the metal does not 'lie below the lowest triplet state of the ligand moiety.15 Idealized potential energy surfaces illustrating photophysical processes in octahedral complexes OF Cr (111): . modifying the ligand or by varying the geometry.10) which is formally Laporte forbidden. characteristic fluorescence and phosphorescence of the latter may be observed under suitable conditions. emission is c o n h e d to 63 (Cr3+.5 dimensional hypersurfaces will be required which is not ~ossible here. Some photophysical processes in Cr (111) octahedral complexes are represented by idealized potential energy surfaces in Figure 8. The ion U02++is also highly luminescent. (6) emission from 4 Tag and (7) emission from aE. Ks[Co(CN). Osa+ and Ifl+).] is highly luminescent. Co3+) and d6 systems (Ruq. corresponding to T. The 4.6.] (ClO. in water-methanol glass (ii) 3(d. 8.16 ~haracteristics of phosphorescence spectra from inorganic com- plexes. or nonrad~ative return to ground state. Tbs+ when cOmplexed with bidented ligands emissive transitions occur within the metal-energy levels (Section 6..

Cl. Cr(urea). The irradiation of monosubstituted car- + from Oh symmetry and consequently for atquation decreases from 0. 22 at .+is stable in aqueous solution whereas (Co(NH.2CN- In the case of mixed ligands photoreactivlty may be predicted empiri- caUy from considerations of the ligand field strength (Adamson s rule). IL rates of aquation reaction depends strongly on basicity of X-. X)2+ of transition metal complexes. The ratio of #NHJ$NCS-is the position of its respective ligands in the spectroche:nicnl series will wavelength dependent. ( d ~ y ) ~ .1 N H. e photosensitization of this aquation can also be initiated by energy Sometimes . (C2H5)3N or other The CrA NH. in presence of O. 8.33 for quartet state.O)w + NCS.O -% + C$+ L6 (H20) L (i) Photoanation reactions. NCS- such considerations.2 Photochemical Processes @erefore it can be concluded that NH. the Ruby laser (Figure 10. Mo(CO). No apparent degradation of biacetyl . and H 2 0 are @versed in the thermal and phorocnernical reactions. orbitals with d-character. and (C) redox reactions. (CH3)2NH. + H. Deuterium substitution has large effect on nonradiative urn (quartet band) and 8 at 652 nm (doublet band). hexammine compla t o less than 0. may occur from these states must be zero to enable them t o compete effectively.6. Cr8+L. For example. both NH. complex. Biacetyl as sensitzzer : phosphnrescence quenched .O):+ + C1. ---t Cr(H. release occurs from T.).14). important solid state laser system.from 2Eg state.n") and 3(n.L CO + where.NH.CN. (C2H5)NH2. Photosubstitution reaction^ can be aquation. involvra heterolytic cleavage of Cr . (NCS!" in 0. hv (i) Photoaquation reactions of the type Co(CN):. For example. nitrate: acetate is 10. 8 for doublet state.g and qE. hence triplet stare of the sensitizer is involved. (Reinnecke's salt) and reactions. efficient pnotochemical aquation reaction c~(H.+. flCr(NHs)JH. Kelqtive laolrities of the tfgand NH. The system deviates (iii) Photosubstitution reactions. (B) rearrangement The photoaquation of KCr(NH3)2 (SCN). fluorescence not in the emission orbital..(d . Emission from C 9 + is the basis of one of the most release decreased. For transition metal complexes both 4T2gand 2E. causes the formation of &substitutedcomplexes : (M = metal. the ratios being 13 at 373 nm (quartet band). The energy delocalized orbitals and . C~(H. (H20) (NCS)" +.O). The role of metal complexes as queachers of &) Acridinium ion as sensitizer : fluoresence quenched . the free ligand values also reflect the contamination of the molecular I #NH~/~JNCS-) 100. (ii) For 01. anation or ligand exchange. the activation energy for the reactions that &dergoes moderately rapid substitution of water for the acid group X-. + L -+ hv Mo(CO). \c~(NH.. For CO(CN).the photoreaction A.0)..SO.0)5(NCS)2+ + H.O occurs when the 4T2. + is without complications and occurs with high quantum yield 4J = 0. The pentacobaltic complex may u ~ ergo d further substitution.).002 for @r(NH. (H20)2. states can be photochemically active but may follow different chemical pathways. presents two aquation modes : ammines.).C12+ + H20 This happens for C~(NH.released although NH. Because of the fast nonradiative deactivat~onof low lying energy states CO(NH~). + + dpy (iY> Fe(CN). The shift of r reactions have helped to identify the details of this aquation the chelate emission from that of the free ligand increases in the sequence Rh(II1) < Ir (111) < Ru (11) and reflects increasing d-orbital participatlo.. for ple. processes.L bond. 4T. and excited states of x-electrons in organic compounds can be rationalized from NCS.) (H. release of NH. The decrease in the chelate emission lifetime from affected . Efficiency hv decreases as the energy difference AE between these two states decreases.3 for bony1 M(CO)n-l L in presence of excess of L. state lies significantly above the VE.states are photoactke. L = ligand). (CH3)3N. state and NCS.x * ) states are said to be derived from r from biacetyl and acridinium ion in the same solvent. #NHI/$NCS-. predominates .(d-d) state from localized orbitals. coordination compounds: (A) substitution reactions.31. ---+ Co(CN). can be used as efficient actinometers between the range 316 and 750 nm. For the specific case of hv Cr(lI1) complexes of Oh symmetry.+ on successive aquation. the axis having the weakest a\ erage field as determined Both. The difference in behaviour between Cr(II1) and Co(II1) ammines may be due to necessity for energy of activation Three fundamental types of phot~chemical reactions are known for In the transition state for reaction with the latter. state. (9 Another example is: F~(cN):.. : 1.). L = NH3.o)~++ NCS. ASPECTS OF ORGANIC AhD INORGANIC PHOTOCHEMISTkY 273 dependent. --+ Cr(H.

the ligand of greater field strength wiil preferentially be replaced.No21 (i) Geometrical isomerization / /"\ \ d-d redax/ \isomerization Cis-bis (glycinato) Pt (11) -+ trans-isomer / \ band d L Cow + 5NH3 + NO. If the labilized axis contains tu.)..O ---t Fe3+ + OH.)~(N0J2+ in O. (iii) Linkage isomerization. CIZ+.12) -ferrioxalate actinometer. When central metal ion becomes strongly oxidising on irradiation in the cis-singlet tetrahedral trans-singlet ligand field band (d-d). I N H C ~ O ~[co(NH~)F.17 Photoracemization in Pt(1Il) complex. This complex exhibits CT and CTLM character at 239 md 325 nm and a ligand field band at 458 nm. I N H.0 '0 d-d tmld u. (iv) Photoexchange processes C.0 different ligands. the stronger field ligand NH3 is lost along NH3-Cr-CI axis. The irradiation at the CTLM bands is more likely to result in photoreduction of the general typr hv (Mz+L. i 1. . The transformation is photochemically allowed but thermally disallowed from symmetry considerations.-Cr-NH. such transition may bring about photo-oxidation: hv Fez+.H. (NO)" + CN*. Lowering of symmetry of the complex will also affect r@n$ and then cage recombination of the two fragments by means of a the nature of reaction due to switching of states. ++ cis rhe photoprocess involves intramolecular twist mechanism without bond cleavage. -0 n .-Cr-C1 NH. This reversible photoredox reac!ion bas the possibility of of light energy into electrical energy. (reaction (i)) is a . and (iv) ligand rearrangement. it can lead t o intramolecular reduction of the ground state intermediate ~ I U U I I state ~ triplet state central metal ion (ii) Racemization (ii) hv CO"' (NH3).)*+ - h e reaction shows deuterium isotope effect. For example. P ME ASPECTS OF ORGANIC AND INORGANIC PHOTOCHEMISTRY be labilized. 12" ---+ CoZ+f SNHa I + The photodecomposition of ferrioxalate in 0.hv Photo-oxidation-reduction or Redox-reactions. axis is labilized rather than Furthermore.f H hv b o t h e r example is Fe(thionine)" y+FeS+ semithionine which reverses dark the dark. CO-ON0 bond. Co(NH. Co(CN). The reactive intermediate is a triplet state of pseudo- tetrahedral geometry.the NH.). Photorearrangement reactions may involve: (i) geometrical is~merizatio~. CO(NH~)~(NO. IN (solid) (NH3)5C~(-ON0)2+ The nitro-nitrito photoisomerization occurs in solution through an ~ ~ t r m o l e c u l amechanism r involving the homolytic fission of Co-N& these predictions. CT and d-d (ii) recemizatidn.. . upon irradiation of Cr(NH. Co(CN*). In some low-valence hydrated cations. (NO)3- A photo-oxidation- + CN- reduction process in solution may be intramolecular when the redox reaction occurs betweeri the central metal atom and one of its ligands or Sntermolecular when the complex reacts with another species present in the solution. 1)L + oxidation products of L Figure 8.Very useful chemical actinometer for tlie near uv and the visible region upto 400 nm ( 4 N 1. B. (ONO)'+ trans.SO. - CO(NH.)zb + M('-l)+ + (n. Steric arid solvation effects may cause deviations from p) Linkage photoisomerization 4.

+ H. The molecule relaxes by emission of radiation* In such reactions chemical energy is converted into electronic energy. In halogenated solvents at room reaction may be a complex with a central metal ion of different oxidation rnperature.lO-phenanthroline and few other complexes when react wltn OH. m Metallocenes act as good quenchers of triplets whose energies lie excitation it is likely to hide a low lying reactive CT type band under its envelop. They are good sensitizers of cis-trans isomerization. it f o r m a CT complex Intermolecular photo-oxidation-reduction reactions involve a light initia- ted electron transfer between a complex and any other suitable molecule available in the medium. If the central ion can give a stable complex with one w a g n e t i c ferrcene is light stable to visible and uv but decomposes in Iower (or higher) oxidation number.3 Photochemistry of Metallocenes not expected ot d-d band and if redox reaction does occur under such -F. solutions of ferrocenes are stable in the dark but on exposure number. This is a CTTS type of transition.% methyl-1. decomposition occurs at a relatively rapid rate. The photoejection of electron may also occur if CTLM band increases the charge density towards the periphery of the complex. Such a reactivity is &. The excitation is in tbe ligand field band. Examples : relracyanoathylene forms a rr-iype complex with ferrocene (I). The tion of the ligand. An oxidized or a reduced form of rhe complex may be obtained. The general reaction scheme is Metal (ligand)(n+l'* + el-] (from reductant) -+ Metal (ligand):+ + hv .O -+ ~e (cN)~' + e3. &tween 280 to 177 kJ/mol-l.l h ~e (cN)~. In the second exalnple. .. generate enough thermal energy to promote it to an electronically excited state. Ru (111)-2. to light. no decompsit~onof the complex occurs. ASPECTS OF ORGANIC AND INORGANIC PHOTO6eHEMISTRY The excitation leads to homolytic M-L bond fission. Another metallocene is bis-benzenechromium iodide (11) a sandwitch type complex.Chemiluminescence in ruthenium complexes. an electron may be ejected to the solvation shell leading to the formation of hydrated electron e.or hydrazide. Quenching rates are nearly diffusion It is not necessary that the reaction should always lead to decomposi. If the new complex species is unstable. .. a decuuiposition reaction may then follow. the prodttct of a intramolec~~larredox p e n c e of 4 is an acidified solution. iontrolled.2' bipyridyl-5 liii) . In CCI.. When the new complex is stable.

k E CURRENT TOPICS IN PHOTOCHEMISTRY

A hazard still awaited primitive life at this point. Oxygen formation
279

to the photochemical production of ozone, lethal to organisms. Their
stence in the depth of the sea must have been important. ,However, with
2 rzspiration, cells fed and multiplied rapidly, until a high
eric concentration of oxygen was reached. Ozone formation was
NINE w confined to the upper atmosphere; its formation requires the very
velengths absorbed by oxygen but its photodecomposition is
"used by longer wave ultraviolet capable of damaging proteins. ?he
\pone layer by absorbing radiation of A < 300 am acts as a safety screen
Some Current Topics in :'@r
d existence of life on the earth. Therefore our concern about the
pssible effects of pollutants such as from the exhausts of supersonic
Photochemistry '~bircraftwhich can disturb the ozone concentration in the upper atmos-
here is very pertinent. Nearer the ground, photochemical reactions
'wween combustion products of motor vehicles, oxides of nitrogen
h d sulpher, aerosol vapours etc. present hazards to the living system
"Section 7.4.1).

9.2 MUTAGENIC EFFECT OF RADIATION
Nucleic acids and proteins are basic chemicals of life. The biopolymer
deoxyribonucleic acid (DNA) is the information containing molecule of
high molecular weight (N 10" dalton) and is responsible for the propaga-
tion of life itself. It is composed of four bases, adenine (A), guanine (G),
thymine (T) and cytosine (C) attached to sugar-phosphate backbone. Two
such strands form a double-helix held together by H-bonds between the
9.1 ORIGIN OF LIFE bases. The base pairing is very specific, adenine pairs with thymine
Photochemistry has played a vital role in earth's history. Long before (A-T) and guanine with cytosine (G-C), which assigns the double
life evolved, the atmosphere was of volcanic nature, consisting chiefly of helix the character of a template.
methane, carbon dioxide, water vapour and nitrogen. Very short wave- All these bases absorb around 260 nm. Thymine and cytoslne are
length ultraviolet light from the sun dissociated these molecules into very most sensitive to irradiation. Two most important types of photo-
=active radicals. A little oxygen and ozone was formed, but kept at low *mica1 reactions that have been observed for these pyrimidine bases are
concentrations by the radicals. Knowledge of the sequence of events is ~hotohydrationand photodimerization. In vivo systems, interactions between
necessarily speculative, but seems to be as follows. First the radicals m b i n s and nucleic acids can also be initiated by radiations of wavelength
combined to give simple compounds. These dissolved in the sea and by sorter than 300 nm.
further photoreaction formed aminoacids etc. Polymerization occurred. Photohydration occurs at the 5, 6 positions of pyrimidine bases, giving
and colloidal matter formed. After an immense period of time, primitive +hydr*6-hydroxy compound. Cytosine and its various glycosides photo-
cell structure evolved from the colloids and engaged in anaerobic metabo- bdrate readily in aqueous solution as detected from the disappearance of
lism (fermentation), reproducing themselves and consuming other molecules A nm peak and appearance of a new peak at 240 nm. On heating, loss
available. Pigments appeared, leading to chlorophyll formation. rates the original molecule. When this photoreaction
critical period was now approached. Anaerobic photosynthesis produce' base pairing is prevented leading to mutation.
oxygen, so that fermentation was replaced by oxidative respiratioo with * zation occurs between pyrimidine bases when they are
forty-fold increase in chemical energ" gain. These events musf have t m suitable geometry in the helical DNA molecule. Thymine is
happened in shallow water (5-10 metre deep) when dangerous ultraviol' t susceptible to photodimerization which occurs at A 280 nm. The
light was cut-off and yet visible light could penetrate. The optical
asymmetry of biological compounds perhaps suggeits that one single
a t this stage was the parent of all future developments.

280 FUNDAMENTALS OF PHOTOCWEMIS~R~ SOME CURRENT TOPICS IN PHOTOCHEMISTRY
28 1
reaction is photoreversible and monomerization occurs by irradiation with ~hlorophyllb also transfers its energy to Chl a, which has two absorption
210 nm radiation. peaks, one in the blue violet region (1 = 448 nm) and the other in the red
All these photoreactions caused by uv light prevent H-bonding between figion ( h = 680 nm) (Figure 9.2). In vitro it emits red fluorescence
base pairs which is fundamental to the replication and propagation of life ( h c i = 680 nm). This characteristic fluorescence is the only fluorescence
(Figure 9.1). Some of these damages can be repaired, others are per. observed, whichever is the light absorbing molecule. This indicates that
manent and lethal t o life. Therefore the importance of ozone screen io other molecules transfer excitational energy to Chl a and the photosynthetic
cutting off these deleterious radiations from the solar spectrum. process utilises a low energy quanta corresponding to red light only. In
~ j l r o , fluorescence efficiency of Chl a is 4~ -- 0 . 3 but in vivn, it is much
reduced. Any factor which tends to reduce photosynthesis enhances $f.

I
Hydrat~on
H
product

\ '
A-----T- Prote~n
Cham p cross l ~ n k
break \

Figure 9.1 Mutagenic photochemical reactions in DNA helix, -___ Chlorophyll A
*
5-hydro-6.hydroxycytosine and thymin dimer. - ..-.-..., ----
0 Chloropnyll D

-
C h l o ~ o p h y l l8
------ Chlorophyll C
Bacter~ochlorophyll

Sunl~ght
9.3 PHOTOSYNTHESIS Figure 9 . 2 Chlorophyll mo1e:ules and absorption spectra of the pigments,
In a broad sense photosynthesis in plants is a photoinduced electron The net reaction of photosynthetic process i n plants is given as
transport reaction. Chlorophyll molecules in the green plants are the hv
n C 0 2 f 17 H,O -4 (CH,O), S-:I Cay
main light harvesting molecules. They are assisted by carotenoids and 680 (9 1)
phycocyanins in this act. These molecules have absorption in the visible chlorophyll
region covering the whole spectrum from blue to red. The energy a b s o r ~ ~ The energy equivalent of red light is about 190 kJ (45 kcal) mol-I, but
by ail thrse molecules is transferred to chlorophyll a (Chl a), which is
a e actual energy requirement for the reduction of 1 mole of CO, to carbo-
b ~ d r a t ein 470 kJ (= 112 kcal) mol-I. This shows that the mechanhn~ of
main light sensitive molecule, by mechanisms discussed in Section 6.6.*

Q ~ I E CURRENT TOPICS IN PHOTOCHEMISTRY 283

reduction of CO, is much more complex. In the initial act of electron
tlansfer process from photoexcited Chl a, H,O serves as an oxidisable Bound F e-S Proleln
substrate producing 0, and also as an electron source for the reduction 0.0
4 F eirtdoxin
of CO,. Two quanta are required to create one oxidized and one reduced
Plaslq~nme
specics i.e. for transfer of one electron. Therefore for evolntion of NADPH
1 molecule of O,, four electron or 8 quanta of light are required
.O

-
Y

sS
g- I Calvin
x
iD \ cycle
The reduction of CO, -+ carbohydrate, is a dark reaction which occurs = P IaSNCV

in a number of enzymatic steps.
Thus photosynthesis is a cooperative process in which light quanta are
t
pooled in the reaction centre by various light harvesting pigments. From
( 4 photonsl
quantitative studies ~t has been established that a set of 3000 molecules of
Chl a could initiate the chemistry needed for evolution of one molecule of
0,. If one quantum is responsible for one photochemical act it can be Figure 9 . 3 Photosynthetic cycle and reaction centres PS I and PS 11.
estimated that a single quantum absorbed in a set of 3000/8 or 400 Chl a
n~oleculescauses just one oxidation-reduction event at the reaction centre. storing a part of it as phosphate bond of ATP (adenosine triphosphate)
Thus the concept of photosynthetic unit can be defined as one in which about through the reaction:
400 molecules of chlorophyll serve one reaction centre. The chlorophyll
molecules in the reaction centre differ in their environment from the ADP
(adenosine diphosphate)
+ (inorganicPiphosphate) + (adenosineATP
triphosphate)
antennae or light harvefting chlorophyll? and hence differ in the absorption
(9.3)
wavelength. It is 700 nm in green planto and 870 nm in bactersiochlorophyll
vhich are designated as P 700 or P 870, respectively. About 30 to 34 kJ (7 to 8 kcal) mol-I is thus stored. The strong reductant
From a study of w a ~ l e n g t hdependence of photosynthesis, Emmerson ob- transfers an electron through a number of enzymatic steps to NADP+
served that the efficiency dropped in the red region (red drop) of the spectrum. (nicotinamide adenine diphosphate) to form NADPH. The intermediate
But if the system was irradiated with blue and red light simultaneously, effi- enzymes are complexes of iron-sulpher proteins such as ferredoxin and
ciency was regained. These observations led to the idea that twophotos\stems hydrogenase. In absence of 0, or low concentration of CO, hydrogenase
are involved in photosynthesis, they are termed PSI and PSII. Cooperation can liberate molecular hydrogen. The reduced NADPH then utilizes the
between thesc t v o systems is necessary for efficient working of the photo- energy stored in high energy phosphate bond of ATP for the reduction of
synthetic cycle. Photoexcitation in PSII creates a strong oxidant and a CO, to CH,O in a number of dark steps. The reaction sequence in which
weak reductant. The strong oxidant is of the nature of quinone and accepts CO, is first added to a five-carb~nsugar was elucidated by M. Calvin and
electrons from water to liberate 0,.A binuclear manganese complex is his associates and is described as Calvin cycle.
supposed to act as a catalyst in the oxygen evolution process. The redox Photosynthesis in plants occurs in thylakoid membranes. These are
potential of the oxidant is between 0 . 0 to + 0.12V. Thus a potential famellar structures, several microns in linear dimensions and are organized
gradient of 0 . 6 to 0 . 8 V is created since E: at pH 7 for the couple stacks in green leaf chloroplast. There are regions of greater density
O,/H,O (reaction 9.2) is +O. 8 V (Figure 9.3). which are called gra,la as different from stronla. By the action of deter-
The trap P 700 in PSI is a special kind of Chl a and is present in the Bent on isolated chloroplasts it has been demonstrated that PSI and PSII
+
ratio of 1 : 300 in the reaction centre. Its redox potential is 0.4 V. In tbe centres are located in different parts of the membrane. Chlorophyll
primary photoact in PSI, a strong reductant and a weak oxidant are molecules are flat molecules with a conjugated system of double bonds
formed. The weak reductant of PSI1 and the weak oxidant of PSI are coupled consisting of 4 pyrrol rings joined in a circle and attached to a long hydro-
through a number of different cytochromes of graded redox potentials carbon chain (phytol chain) (Figure 9.2). Through this long chain the
ra~lgingfrom E; = 0.0 to + 0.4V. During the downhill electron transfer light absorbing molecule is attached t o the lipoproteins of the membrane
over the enzymatic chain some amount of energy is degraded, simultaneously in regular ordered arrangement. The membrane plays a very ilnportant

SOWE CURRENT TOPICS I N PHOTOCHEMISTRY 285 role in imparting unidirectionality to the electron transport by separating the oxidation and reduction centres.Chl+ -t A.. the membrane preventing back recombination: MEMBRANE Direction of electr~cf ~ e l d ______) Figure 9. pump for transfer of electrons 'uphill' from electronic levels of the donor to electronic levels of the acceptor.+ h:. It has be:n possible to mimic the energy conversion and storage Here Chl denotes a photosynthetic pigment.. (. The coupling is not by chemical sub. It has been pointed out that the primary quantum conversion apparatus in photosynthesis behaves in a way very similar to photoconductive semiconductors in that the impinging light separates positive and negative charges as electrons and holes. A physicak separation of electron (-) and the positive hole (+) or oxidant is brought about. -t=positive hole. A . A photoelectrochemical Chi+ with positive hole (+)constitutes a strong oxidizing agent and should cell can be constructed by placing two redox couples of graded potentials be capable of oxidizing compounds with fairly high redox on either side of the membrane and dipping m:tal electrodes in each of (Figure 9. + + D+ Chl.4). The light energy is sto:ed in the form D .H 2 0 reduction product in anothercentre. h:q or Chl+ $H. Such ideas have initiated iu ~ ' i l r ostudies of chlorophyll-sensitiz2d reactions in photosynthetic membranes from the laws of electrochemica I Chl.Chl+ + the oxidation product being formed at one enzymatic centre and the e.O+ + + C ~ I H+ 20.Chl.Chl. stances but by electrochemical states. increases the efficiency of charge separation at excited chlorophyll molecules. Chlorophyll itself is not decomposed> H. A-=Chi+ . (b) Illustrating energy levels of ground and excited states of pigment molecule in separation. them. I Pigmented membrane I The membranes are composed of lipids. They are prevented from recombination by the hydrophobic The alternative sequence of reactions initiated by light can be interior of the membrane. A cooperation of a suitable electron acceptor and a donor the membrane and acceptor and donor molecules in solution. h:q is hydrated hole.+ D+ Chl.Chi.Chl+ A. +Chl+ + 2Chl hv' kinetics. The exciton migrates through the photosynth:tic Summarized as follows : unit until it meets an oxidizing enzymatic centre which serves as a trap for the excited electron. is hydrated electron. They provide a potential gradient for the transfer of electron across the membrane from PSI1 to PSI.O . an exciton.+ e. AG=nFE is theoretically available electrochemical free energy. photocurrent is The combination of excited electrons and the hole left behind is called generated on excitation of the membrane by light energy. On completing thc circuit by suitable device.+ (exciton formation) then migrates through the units until it reaches an electron donating centre- H 2 0 . The oxidized chlorophyll molecule (BLM)formed from chloroplast lamella extracts. + A + A. + of chemical energy in the reduced form of the oxidant. p*. e.+) is a n electron-hole capacity of these membranes by experimental bilayer lipid membraneS Pair or exciton. + Chl+ The primary photochemicai oxidation-reduction process is thus completed. Under these conditions. The exciton is now reduced to a free hole which Chl hv + Chl. these molecules act as photon-powered electron e=electron.+ Chl- but only sensitizes the reaction. pigments and protein complexes.4 Membrane model for electron transfer reaction in photosynthetic cycle with acceptor A and donor D on either side of the membrane (a) P. F+ are respectively norinal state electronicaliy excited Thus in photosynthesis the initial events are a light stimulated charge state and oxidised fern of pigment molecule.

------ occurs through channels provided by a compl