Photochemistry of Small Molecules - Hideo Okabe

PHOTOCHEMISTRY OF SMALL MOLECULES HIDEO OKABE National Bureew of Standards A. WILEY-INTERSCIENCE PUBLICATION. + JOHN WILEY & SONS NEWYORK + CHICHESTER + BRISBANE + TORONTOCopytighigo 1974 hy John Wiley & Sous, Ine Al sights eoxerved, Published simultaneously in Cunt Reproduction o¢ translation of any part of this work beyond that permitted by Sections 107 ve 10% of the 176 United States Copyright Aet without the permission ‘the copyright owner iv unliwful, Requests for perimsion or further information should be addressou to he Petmissions Department, aha Wily & Sons, Ine Library of Congress Cataloging in Publication Dat Okabe, Hideo, 1923 Photochemistry of small molecules. ‘A Wiley-Intersienee publication Bibliography: p Includes inden 1 Photochemistry. 1. Til yoras 20 savas 7.0706 ISHN O71-6808-7 Panto in the United States of America WoT esaat Preface This book has been written in an attempt to cover the remarkable progress made in recent years in the field of photochemistry of small molecules with up to five atoms in the gas phase. The advancement of flash photolysis-kinetic spectroscopy, laser tech- nology. and other new techniques has made possible the detection of photochemical primary products and detailed studies of photodissociation dynamics. The secondary processes of atoms and radicals formed in the primary process have also been studied extensively. The reactivities of electronically excited atoms (C, O, 8, ete.) and radicals (C0, CH, ete.) have been found t be very different trom those of corresponding ground state atoms and radicals. The results of these studies, together with the aditional end product analysis and quantum yield measurements, have greatly aided in our understanding of the photochemical processes, particularly for small motecules. These recent developments, as well as the underlying principles, are described in some detail in dealing with the photochemistry of about 80 small molecules Studies of (he photochemical processes of small molecules are not only of intrinsic interest but also are important in understanding the photo: chemistry of isotope enrichment, of air pollution in the troposphere and stratosphere, and of the atmospheres of other planets This book is aimed at the physical chemist, spectroscopist, and :umo- spheric scientist interested in photochemistry. As a reference book it lists about 1200 papers, including some original classic studies and those of recent years up to July 1977. The space limitation and the tremendous amount of publication in the last decade have prevented inclusion of some important papers, | apologize to those whose work has not been quoted. Since the photochemical reaction iy initiated by absorption of light in the visible, ultraviolet, and vacuum ultraviolet regions, an understanding of atomic and molecular spectroscopy is required, Chapter 1 gives a brief Inteoduction to the electronic states and transitions in atoms sind simple molecules, The primary photochemical process brought about by light absorption isdealt with in Chapter 11. A preat des dlynannies (sue ts Hhtriatomic molecules. Quantum mechanical theory dealing with dynamies of Photodissociation has been proposed by many workers, Various experimental techniques of photochemistry are deseribed briefly in Chapter WL. Further details are given by Calvert and Pitts (4), Noyes 4 (22), and McNesby et al. (685a), Production, detection, and reactivities of various electronically excited atoms are given in Chapter IV. The importance of electronically excited atom reactions in photochemistry has been recognized only recently Photochemical processes and electronic states of simple molecules with Up to five atoms and radicals with up to four atoms in the gas phase are covered in Chapters V through VII. The absorption coefficients available for many molecules are shown in figures, as they are important in understanding the quantitative aspect of photochemistry. Bond dissociation energies given are calculated mostly from enthalpies of formation of atoms, radicals, and molecules tabulated in the Appendix Finally, enrichment of isotopic species huts been achieved for a number of atoms and molecules using an appropriate monochromatic light source that preferentially excites an isotopic species of interest in mixtures of other isotopic species. The photochemistry associated with isotopic enrichment is briefly described in Chapter VIII. Great efforts have been made recently to obtain information on the detailed photochemical processes involving smog formation, stratospheric pollution, and atmospheres of other planets, and brief discussions of these subjects are also presented in the chapter. | would like to express my appreciation to Professor W. A. Noyes, Jr.. who introduced me to the field of photochemistry and to the late Dr. E, W. R Steacie, the late Professor W. Groth, and Professor J. R. MeNesby, who aught me various aspects of photochemistry. I am particularly grateful to Dr. R, E, Rebbert who has carefully read Chapters 1, I, and VII and to Dr. A. H. Laufer for his critical reading of Chapters II! through VI and VIL Their numerous suggestions have greatly improved the manuscript Thanks are due to Dr. M. D. Scheer for his continuous encouragement ‘and to many friends and colleagues, especially to Des. 1D Garvin, PJ Ausloos, R. F, Hampson, M. Krauss, and V. I, Dibeler and Professor J.P. Simons for their help and discussion during the preparation of the manuscript, | would like (0 thank Professor S. A. Rice at the University of Chicago who has given me the opportunity to write this book. I am in- debted to Mrs, P. A. Davis who did an excellent job in typing the entire manuscript. ind Leighton Hive Oxane Gaithersburg, Maryland March 1978 Contents INTRODUCTION 1 SPECTROSCOPY OF ATOMS ULE Electronic States of Atoms, § ‘Atoms with One Outer Electron, § ‘Atoms with More Than One Outer Electron, 7 tum States of Diatomic Molecules, 8 Rotational Energy Levels af Diatomic Molecules, 8 Vibrational Energy Levels of Diatomic Molecules, 10 Electronic States of Diatomie Motecules, 11 Coupling of Rotation and Electronic Motion in Diatomie Molecules: Hund's Coupling Cases, [2 intum States of Polyatomic Molecules, 14 Rotational Levels of Polystomie Molecules, 14 3 cuapr ERI AND MOL 1 Vibrational Levels of Polyatomic Molecules, 15 Blectronie States of Polyatomie Molecules, 16 ion, 18 hermal Contribution to Photodissoci 1-41 Vibrational Population in Diatomic Molecules, 18 142 Rotational Population in Diatomie Molecules. 19 14.3. ‘Thermal Contribution to Photolysis and Fluorescence, 20 1-8 Electronic Transition ia Atoms, 22 1S. Finstein Transition Probabilities, 23 1 5.2. Absorption Intensity of Atoms, 24 1 5.3. Oscillator Strength, 28, 1-6 Resonance Absorption and Ennission by Atoms, 27 16.1 Line Profile in Resonance Absorption: Natural Doppler and Pressure Broadening, 27 16.2 Line Profile in Resonance Emission; Four Types of Resonance Lumps. 31 16.3 Measurement of the Absorption Intensity Using Resonsnee Lamp, 38 1-7 Band Intensities in the Motecolar System, 37 La Coefficient in the Molecular System, 41 PML The Beer-Lambert Law in the Molecular System, $1 182 Deviation from the Beer-Lambert Law, 1X2 Measurement of the Integrated Absorption Coellicient, 44 [84 Temperature Dependence of the Continuous Absorption Spectrum, 44sili Contents 1-9 Electronic Transitions in Diatomic Molecules, 46 row tional Structure in the Electronic Transition, 47 192 ‘ranck-Condon Principle, 47 1.9.3. Rotational Structure in the Eleetronie Transition, 4 [-10 Selection Rules in Atoms and Molecules, 0 TI0.1- Selection Rates in Atoms, 50 1-102 Electronic Transitions in Diatomie Molecules, 31 1.103 Electronic Transitions in Polyatomie Molecules, 91 RH: PRIMARY PHOTOCHEMICAL PROCESSES E MOLECULES, The Primary Processes in Diatomic Molecules, SH HLL Spectroscopic Studies of Dintomie Molecules, $8 111.2 Photochemical Studies of Diatomic Molecules, 61 1-2 The Primary Processes in Simple Polyatomiie Molecules, 64 112.1 Fluorescence in Simple Polyatomie Molecutes, é- 1 22- Photodissociation in Simple Polyatomie Molecules, 6 1 2.3. Predissoviation in Simple Polyatomic Molecules, 6 11-3. Correlation Rules in Photodissociation, 71 13.1 Examples of Spin Correlution Rutes, 71 M32 Examples of Symmetry Correlation Rules, 73 H-4 Distribution of the Excess Energy in Photofragments, 81 14.1 Measurement of the Translational Energy of Photofragiments, 82 11-42 Measurement of the lnternal Energy of Phototragments. X6 Angular Distribution of Photofragments, 88 Models for Energy Partitioning in Photodissociation, 92 IL 6.1 Statistical Model, 92 11 6.2 Impulsive Model, 93 11.63 Equilibrium Geometry Model, 94 164 Other Models, 95 1165 Rotational Excitation, 96 ation of Bond Dissociation Energies, 97 17.1 Determination of Bond Dissociation Energies from Thermochemical Data, 9X 117.2) Determination of the Bond Dissociation Fnergies in Diatomie Molecules, 100 117.3 Determination of the Bond Dissociation Energies in Simple Polyatomic Moles, LL cuapt IN SIMPI i CHAPTER Il: EXPERIMENTAL TECHNIQUES IN PHOTOCHEMISTRY MIE Light Sources, 107 HUT Atomic Line Sources in the Vacuum Ultraviolet Reon. 108 107 m2 m3 us Contents ix HL 12) Atomic Line Sources in the Ulraviolkt and Visible Regions. HIT ILL Molecule fund Sources, 113 MEL Lasers, 16 Materials for Photochemical Stadies HE 21 Window Materials, 119 ME 22 Filters, 121 Quantum Vields, 121 HL 3.1- Detinition, 121 ME 3.2. Calculation of the Primary Quantum Yield, 123 ‘Actinometry, 125 HA. Chemival Actinometers in the Vacuum Ultraviolet Region, 126 42. Chemical Aetinometers in the Ulteaviolet Region, 127 nation of the Elementary Reaction Rates, 128, MIE 5.1 Pscudo-tirst-Order Devay of Reactive Species, 130, MI 5.2. Second-Order Decay of Reactive Speci HI 5.1 Time Dependent Radical Concentration by Consecutive Reactions, 133 Determination of the Primary Photochemical Process by Radical Trapping Agents, 135 HE 6.E Examples, 16 ny CHAPTER IV: PRODUCTION AND QUENCHING OF ELECTRONICALLY EXCITED ATOMS 1B9 IV-1 Fluorescence Quenching in Atom ‘Quenching Cross Sections, 139 1-2. Mercury Sensitized Reactions, 144 IV21 Nyc) + Hy, 145 IV 22 MeO P y+ Ny Mpc?) + CO, 145 W 23 1eP) + 1GO, Het) ENE, 46 IV24 NgeP,) + Paraffin, 146 IV 25° 11RC'?,) 4 Olefins. a6 IV 26 Hg!) Senstized Reactions, 146 IV-¥ Other Atom Seastized Reactions, 147 WAL CUPP). 1) Sensiizad Reactions, 147 IW 42 CP) Sensitized Reactions, 147 IV 3.3. Na? Sensitized Reactions, 147 IV 34 An) Sensitive! Reactions, 148 IV 33 KeOPi. 12) Sensitized Reactions, [48 IV 1.6 Xe(*?)) Senstized Reactions, 14k IV-4 Reactions of Metastable O Atoms, 149 IV. OUD) Atoms, 149 TV 42 O('S) Atoms. 152 IV-S Reactions of Metastable § Atoms, 156 IVS Se*Dy Atoms, 156 IW S2 SCS) Atom 18Wv-6 wa Reactions of Metastable and Ground State © Atoms, 187 1V-6.1- CCD) Atoms, 187 1V-62. CUS) Atoms, 157 WV 63 CUP) Atoms. 159 Renctions of Other Metastable Atoms, 159 ITE NCDP) Atoms, 159 1-72. BrP...) Atoms, 160 173 12M) Atoms, 160 I-74 Ase, 2P) Atoms, 160 IV-75. Sat'Dy.'8) Atoms. 16 176 Pht, '3) Atoms, 161 CHAPTER V: PHOTOCHEMISTRY OF DIATOMIC MOLECUL 162 Hydrogen, 162 Hydrogen Halides, 162 V2.1" Hydrogen Fluoride, 162 V-22 Hydrogen Chloride, 162 V-23 ydrogen Bromide, 164 V-24 Hydrogen lode, 164 Carbon Monoxide, 166 Ve3it Photochemistry, 167 Nitrogen, 168 V-4.1-Photodissociation in the Upner Atmosphere, 170 Nitric Oxide, 171 V-5.1 Fluorescence, 173 V5.2. Predissociation, 179 V-5.3. Photodissociation, 174 V-S.4_NO in the Upper Atmosphere, 176 Oxygen, 177 W611 '0,00E,), 177 ¥-62 0,4a'A). 181 V-63 OMHES), 183 uur, 18 Halogen 185 VeRT Fluorine, 184 V-82. Chlorine, 184 V-8.3 Bromine, 185 V-84 lodine, 187 Interhalogens, 191 ¥-9.1 Bromine Monochloride, 191 V-92 Iodine Monochloride, 191 V-9.3. Iodine Monobromide, 191 Alka fodides, 192 ¥ 10.1” Sodium Fodide, 192 V-10.2 Potassium lodide. 192 Electronic Transitions and Lifetimes of Some Diatomic Radicals, 192 VILL Diatomic Radicals Containing Hydrogen, 193, V 112 Diatomie Radicals Containing Carbon, (Cyano), 197 tatomnic Carbon), 19% vus nic Radicals Containing a Halogen: FO, Ck V. 11.4 Diatomic Radicals Containing Sulfur, (Sulfur Monoxide), 199 (Carbon Monosulfide) 200 1 BrO, and 10,199 CHAPTER VI: PHOTOCHEMISTRY OF TRIATOMIC MOLECULES. 201 vin vir vis vis vis Water (1,0). 201 VELL Photodissociation, 201 Hydrogen Sulfide (HS), 204 VE21 Photodissociation, 204 VI-2.2. Energy Partitioning in Photodissociation of H,S, 205 Hydrogen Cyanide (ICN), 206 VE-3T Photochemistry, 206 Cyanogen Halides, 206 VID Photochemistry, 206 Carbon Dioxide (CO,), 208 VE-S.L Photochemical Reactions, 209 VI-5.2 Stability of CO, in the M4: Carbonyl Sulfide (OCS), 215 VE 6.1. Photodissociation in the Near Ultraviolet (1900 to 2550 A), 215 VI 62 Photodissociation in the Vacuum Ultraviolet, 217 Carbon Disulfide (CS,), 217 I-11 Photochemistry above 2778 A, 218 VI72_ Photochemistry below 2778 A, 219 Nitrous Oxide (N,O), 219 VI-R.I Photochemical Reactions, 223, VIX2 Production of Metastabe Species by the Photolysis of NO. 225 VI-8.3 NO in the Upper Atmesphere, 226 Nitrogen Dioxide (NO,), 227 VL 9.1 Photodissaciation above 3980 A, 230 VI-9.2 Photodissociation below 3980 A, 230 VI-9.3Photodissociation in the Vacuum Ultraviolet, 232 VI 94 Fluorescence, 232 VI 9S Nitrogen Dioxide in the Atmosphere, 235, Nitrosyt Halides, 238 VI 10.1 Nitrosyl Chloride (ONCD, 235 VL10.2. Nitrosyl Fluoride (NOF),237 Wd Venus Atmosphere, 214sib Contents vient vie vers vis Orone (0). 237 VI ILL Photedissociation in the Chappuis Hands (4400 10 $500 A), 240 VI-11.2. Photodissociation in the Huggins Rands (3000 to 3600 A), 240 VE-113 Photodissociation in the Hartley Bands (2000 10 3200 A), 241 VI 114 Photolysis of Oy in the Presence of Other Gives VE-1TS Ozone i the Atmosphere, 245 Sulfur Dioxide (SO,), 247 Vi12,L Specteoscopy and Photochemistry af SO, in the 3400 to 1900 A Region, 248 VI 122 Spectroscopy and Photochemistry in the 260K 10 400A Region, 251 VI 123. Spectroscopy and Photochemistry in the 1H00 to 2350 A Region, 254 VI 124 Photochemistry inthe 1100 to 100A Region, 254 Vi-125 Photooxidation of SO, in the Atmosphere, 259 ‘Chlorine Oxides, 257 VEISE Chlorine Dioxide (C10}). 257 VI-132 Chlorine Monoxide (C1,0),257 ‘Triatomic Radicals; Photochemical Produ tivities, 258 Methylene (CHz), 258 Azidogen (NH3), 261 © Phosphorus Hydride (PI), 262 Ethynyl (CH). 262 Formyl (HCO), 263 Niteoxyl Hydride (INO), 263, Hydroperoxyl (HHO,) and #150 Radical, 263 Triatomie Carbon (C,): CCO Radical. 268 Azide (Ny), NCN Rudieal, NCO Radical. 266 VI-14.10 Carbon Difluoride (CF). 26% VE-14.11 Disulfur Monoxide (5,0), 268 1. Detection, CHAPTER Vil: PHOTOCHEMISTRY OF POLYATOMIC MOLECUL! vu-t vue vues FOUR-ATOM MOLECULES ‘Ammonia (NH), 269 VIE LL Primary Processes, 269 VIL-1.2 Secondary Reactions, 271 Phosphine (PI), 272 Vil 2.1 Photolysis, 272 Acetylene and Haloacetylenes, 273 VIPAT Acetylene (CH). 279 Vil 3.2. Chloroaceiylene (CICHD, 275 269 vig vies vii vir view vis view vit vin views vit vu-ts vite ay viz Contents xis VHA} Bromoacetylene (HCH), 276 VIL AA todoacetylene (ICH. 277 tldehyde (IHCHO), 277 VUE 4.1 Photochemistry in the Near Ultraviolet, 277 VIE42- Photodissociation in the Vacuum Ultraviolet, 280) Diimide (N,H,), 281 Hydrogen Peroxide (11,0). 282 VIG. Photochemistry, 242 Isacyanie Acid (LINCO); Ivothiocyanie Acid (NCS), 283 Eormyl Fluoride (CFO), 285, Nitcous Acid (LINO, ), 246 VIL 9.1 Photodissociation, 287 VIL 92 Nitrous Acid in the Atmosphere, 287 ydrazoiec Acid (LIN,), 287 VIL 11 Photeatissoxiation, 288 Phosgene (OCC) 289 VIE-TLL Photolysis, 249 Vhiophoxgene (SCC), 291 VIL 12.1 Photochemistyy, 291 Vhionyl Chloride (OSC), 292 Cyanogen (CyNy)s 293 Sulfur Monochloride (S,C1,), 294 Foue-Atunn Radicals, 295 VIP 16.1 Methyl (Clty), 295 VII 162 Tritoromethyi (CE): Teichloromethyl (CCI). 296 VIL 16.4 Nitrogen Trionide (NO,). 296 VIL 164 Sulfur Trioxide (SO,), 297 FIVE-ATOM MOLECULES, Methane (CH), 298 Halogenated Methanes, 299 VIL IS) Methyl Chloride (CHC, Methyl Bromide (CHB, 300 VIL 182 Methyl fodidte (CHD. Trifluororoometbane (CF 1), 301 VIL 18.3 Methylene lodie (CHL). lodoform (CHL) Chitorotonn (CHC), 304 VIE IK Trichlorotluorametisiie (CECI, Preon-1 1), Dichlorodifluocomerbane (CFC. Feeon-12), Dibromodifluoromethane (CF_Be,), 304 VIE IK.S Carbon Tetraehoride (CCl) Beomotsichloromethane (CCI Br, 306 VIE 1X6 Dichloroftuoromettiane (CHECL, (Chiloresdituoromedtine (CHE,C, Diaromen sue (CHN), Diavirine (Cyclic CHAN.) 08 Ketone (CH,CO), 49 vienyvu-2i viz vias vii-24 vias vui-26 Formic Acid (HCOOH), 314 Cyanoacetylene (C,HCN), 315 Nitric Acid (HINO), 315 VII-23.1 Photodissociation, 316 Cyanogen Azide (NjCN), 318 Carhon Suboxide (C03), 319 VIL 25.1. Photolysis of CxO, in the Near Ultraviolet, 221 Vi 25.2 Photoljsis of CO, in the Vacuum Ultraviolet, 321 (Chlorine Nitrate (CIONO,), 323 CHAPTER VUE: VARIOUS TOPICS RELATED TO PHOTOCHEMISTRY 325 vat vu-2 vis Isotope Enrichment, 325, VIN-L1 The Atomic System, 326 VIII-1.2 The Molecular System, 328 Photochemistry of Air Pollution, 330 VUII-2.1 The Earth's Atmosphere, 330 VIN-2.2 Atmospheric Air Pollution, 332 VII-23 Photochemical Air Pollution in the Troposphere, 332 VIII-2.4 Ait Pollution in the Stratosphere, 340 Photochemistry of the Atmospheres of Other Planets, 352 VIII-3.1 Photochemistry of the Mars Atmosphere, 352 VIN-32 Photochemistry of the Venus Atmosphere. 356 ViII-3.3 Photochemistry of the Jovian Atmosphere, 157 APPENDIX: REFERENCE TABLES, 361 REFERENCES. 381 INDEX 43 PHOTOCHEMISTRY OF SMALL MOLECUL:138 Experimental Techniques in Photochemistry Table 111-3. Rate Constants of Reactions of Some Radical Trapping Agents with Hand CH, at Room Temperature Rate Constant Reaction em? molec! see") 1 +0; "HO, (N= atm) 1s x to 4 H+ NOSHNO (Ar « 1 atm) Sax 10-8 H+Hl-H +! 026 x 10°10 H+ HBr+H; + Br 27x10 2 Wel-His) OT x 10°" H+ HSH, + HS Ra 10° H+ GH GH, 26x10 8 H+ GH, +GHy 16x10 3+ CH, +0, 4 CHO, (Ny = 1am) 4ctp CH, + NO“ CH,NO (He = | atm) 15x 10°" CH, + HICH, +1 bios CH, + HBr-+ CH, + Be 1S 10 8 Hy +1, + CHL +1 Lacy 24 CH, + HS CH, + HS S419 1% + From Ref. 7 * From Ref 24a McNesby ct al. (683) have used C,Dq as a scavenger of H atoms produced in the photolysis of HO and NH, in the vacuum ultra- et. Since, H atoms react exitemely slowly with HO or NH (<10°'8 cm? molec! sec™') (ref 1) they are effectively eliminated by added C;D,. Thus, the ratio of H, with and without added CD, shows the extent of molecular hydrogen production in the primary process. Ung (984) has used ©, as an H atom scavenger in the 1470A photolysis of HO. The ratio of Hy with O, present to the overall H, yield without O, is 23%,.. From this information Ung estimates that the primary yield of H, production is 8°, chapter 1V Production and Quenching of Electronically Excited Atoms Electronically excited atoms have been known to play important roles in many photochemical reactions. In this chapter electronieally excited atoms are classilied into two groups. The first group of excited atoms are those that are formed by resonance absorption and decay rapidly by Muorescence if not quenched by collisions with foreign gases, Examples are electronically excited Hg, Cd, H, Ar. Kr, and Xe atoms. OF these HgP,) aioms and their reactions have been most extensively studied. The mercury sensitized reactions provide a convenient way to generate atoms and radicals in the spectral region where many molecules do not absorb ‘The second group of electronically excited atoms consists of metastable atoms such as OCD) and O('S). These metastable atoms cannot be produced directly from ground state atoms by light absorption, However, they are often formed in photodissociation of molecules. The production of metastable joms from photodissociation has been known by the different reactivities of the metastables from those of corresponding ground state atoms. From the spin conservation rules sce Section I1-3.1) tis often reasonable to assume the production of metastable atom's in the primary photochemical process, although the direct detection of metastable atoms has succeeded nly recently by optical absorption or emission following flash photolysis fof molecules. Detection is difficult, since metastable atoms usually react rapidly with the reactant molecules and often the detection of the atoms has to be made in the vacuum ultraviolet. Because of their long radiative lives, the main fale of metastable atoms is physival and chemical quenching by ‘gases present in the system, An excellent review on the reactions of metastable ittoms is given by Donovan and Husain (310) The electronie states and the lifetimes of atoms of photochemical interest are given in the Appendix, Table A. 2 IV-1, FLUORESCENCE QUENCHING IN ATOMS; QUENCHING CROSS SECTIONS Electronically excited atoms produced by resonance absorption have a short life, on the order of | to 100 nsec, after which they return to the ground 139140 Production and Quenching of Electronically Excited Atoms state. The resulting fluorescence is called resonance fluorescence. In the pres nce of a foreign gas the intensity of the resonance Auorescerce is reduced (quenched), The quenching of the excited atoms, denoted by A%, may result in chemical reactions (chemical quenching) or the quenching may produce metastable or ground state atoms and translationally or internally excited foreign gus molecules (physical quenching) The sequence of events may be written aSar I, avr At A 4 hy hy av-2) AT+MAA+MOrA4D, + Dr hy av.ay where M signifies a foreign gas, M’ is a foreign gts with excess energy, and Dy and D, are dissociation products, In steady state conditions we have 1, = RAN + AMM) (iv-4) where 1, is the number of photon: absorbed by A per cm’ see”, ky is the natural decay constant of Muorescence in sec" and by, is the quenching Fate constant (cm molec™" sec!) by M. The quantity in parenthesis indicates concent ations. Ifconcentrations of A atom are lrge, the primary Fadiation isabsorbed by A forming A*,and A* emits the secondary radiation, which is absorbed again by A atoms and the process is repeated many times. This repeated process of emission and absorption is called radiation im: Prisonment or radiation trapping, In this case the fluorescence lifetime becomes much longer than the natural lifetime 1/k, and musi be replaced by Lak, (g « 1), Blickensderfer et al, (119) have calculated that in Hg(?P,) «atoms, imprisonment lifetimes are four times as large as the natural lifetime when the optical thickness is 2 that is, g = 0.25. Only when the optical thickness is below 0.1, corresponding to a Hg concentration of 10"? em at path length of 1m, we obtain the natural lifetime (y = 1). Phillips (807) has recently calculated the ratio of trapping time to natural lifetime for N (1200 A),H (1216 A),0 (1306 A), Hg(1849 A), Cd (2288 A), H1g(2537 A), Cd(3261 A), and Na(5890 A) resonance lincs in the atom concentration rat ge 10" to 10" em=*. AC a concentration of 3 x 10" atoms em~* of He, the lifetime of Hgl*?P,)is about 20 psec while the natural lifetime is only 0.11 usec From 1, =kAA®), where I, is the fluorescence intensity (quanta om? see” "We obtain Je =T5y IV-5a) TF yi tM) oe IW-1. Fluorescence Quenching in Atoms; Quenching Cross Sections 81 ICT} and 1, are the fluorescence intensities with and without the foreign gas, respectively. we find yt bys i @ hy where @ is called quenching. We obtain the linear relationship between 1/0 and (M), This relationship is called the Stern-Volmer formula first derived by Stern and Volmer (924) in 1919 for quenching of I; vapor. I'(A) is large, ky must be replaced by gh ly « 1) \ ky “i+ OO thy Hence g must be known (either theoretically or experimentally) to obtain 4 from the slope. The number of quenching collisions per excited atom by the foreign gas M per second, Z, ean be expressed by the quenching cross section a? (em? molec ') in analogy with the gas kinetic collision cross section (Note that o is used before to designate the absorption cross section; see Section I-8.1,) (My (1V-sb) i) (1V-Se} aT Za kyiM) =o? [PT my (v-6) « where R is the gas constant equal to 83143 < 107 erg K~! mol~', and jx, the reduced mass, is defined by Pear aget (v-7) MA” Mo M, and My arc masses of the atom A and the quenching gas, respectively. Some workers define the quenching crass section as (lv) where J(BRT aa) isthe average relative velocity. Hence, oj =na* (v9 ACT = 300°K, 2 the number of quenching collisions per second foreach excited atom by Mis given by 792 x 10% z () av-10) vi where (M) is the number of quenching molecules per em It has been shown [Mitchell and Zemansky (21), p. 197) that the quenching of the Hg 2537 A line by foreign guses follows the Stern-Volmer formula only when (1) Lorentz broadening [see Section 1-6.1] by foreign gases is142 Production and Quenching of Electronically Excited Atoms absent, and (2) the fluorescence consists of the primary radiation, that is, no absorption and reemission of the primary radiation takes place. The second condition is fulfilled only when the optical thickness aq! is near zero. Zemansky performed his experiment under the conditions that remission of the primary radiation cannot be neglected and Lorentz broadening is, absent and he obtained quenching cross sections for various gases by properly correcting the secondary emission. According to Mitchell and Zemansky, the quenching Q is a complicated function of both +Z (x is the lifetime of the excited atom) and the absorption coeflicient a at a given wave number ¥, Hence, to obtain the quenching cross section from the observed quenching Q, it is necessary to know the absorption coeflicient. Since the width of the primary radiation is much broader than the Doppler width of the absorbing gas it is believed that the absorption coefficient changes during the repeated absorption and emission processes, although it difficult to estimate such changes. Samson [quoted in (21), p. 200], on the other hand, has assumed that at low pressures of the absorbing gas the transmission of light at a given wave number may be expressed as “expo? exp —a9l exp(—a)} dao exp(—al) E.gnoten a (IV-10a) P= 0) do where @ is 2(F ~ ¥p)/ATp Vin 2 [see (1-60)]. The quantity @ is the average absorption coefficient and @! is called the equivalent opacity. It is now possible to construct theoretical curves of @ as a function of tZ for various 2l values, Once Q is determined experimentally as a function of pressure p, it is possible to obtain «% corresponding to a given pressure by comparing the calculated Q@ ~ 07 curve with the experimental Q — p curve. From the linear slope of a plot of 2 against various pressures of the quenching gas one can obtain the quenching cross section. The value aja! is 0.665 for ol = 1 and it decreases as al increases Blickensderfer et al. (119) have recently extended the Samson theory to include various vessel geometries under conditions of pure Doppler, pure Lorentz, and Voigt (a combination of Doppler, Lorentz, and natural broadening) line profiles, The quenching cross section can be obtained also by @ dynamic method in which the decay ofthe fluorescence intensity is measured after the exciting light is cut off Ifthe initial fuorescence intensity is 1? and the intensity after a time r is I,, we obtain 1, = Ie thr ha (1V-11a) where ky is the natural decay rate in sec“! without the quenching gas and Aw isthe rate constant of fluorescence quenching by M. tn the case of radiation IW-1, Fluorescence Quenching in Atoms; Quenching Cross Sections 143 trapping, " From the slope of plot In(1)/1,) versus decay time ¢ without M we obtain ‘gk, and with M we obtain gky + ky(M). Using the decay method Matland (669) has obtained for the quenching cross section of Hg(*P,) by Nz a value of o? = 0.16 x 107" em?, which is, in good agreement with o? =0.19 x 10-!*em? obtained by Zemansky (1083) ina static system. Quenching cross sections for Hg(?P,) atoms have been measured for a number of gases by Zemansky (21), Michael ct al, (402, 702, 703), and Horiguchi and Tsuchiya (481). See reviews by Cyetanovié (256) and Calvert and Pitts (4) Some values of the quenching cross section a® are given in Table 1V-1. Since it is difficult to achieve sulliciently low concentrations of mercury to avoid radiation imprisonment, Wexpt—[oky + kM} at (IV-11by ‘Table 1V-1. Quenching Studies of Hg(*P,) by Various Simple Molecules Quenching enh Major (ros Section Siete Prtucr Sem Ret ‘ (ye > 09 036 176, 481 . 02% moo yyy = 080, Oy, < 003 86,98 21,176,702 : og tt 177,703 co 02 07 COW" = 11) 27,74 173,180,408 44, $57, 708 No =02,% 4 ;,9= 061 282,33 481,703 Hal mets Hh 16 0; 2s 708 Hs H+ Ht SH 3 176,256 G, Hy + C85 30 176.256 NO lig +N, +0. 212 176,703 0 ag = OK, 05 143 21,173, 180 HEP) 10" ws NH, py = 062,064 a2 21.173, 40 Hee Pay NU 1% lig-+ NH, + He@ ~ 03) 78 CHa, Cole. CoHly Bye = Ol ~ 08, no HH 36, Het R +H, Hgt?Po)- RHP 173,176,177 cnc Higcl + CH, M4 176,256 Gay gp < 001, Oygy = O18 3 ue 2) formation Fog: sien the quam yield for ECP. sue orn?) Ht REN] which emit continas » Lobse complexes of Hal) with MIHO,144 Production and Quenching of Electronically Excited Atoms quenching cross sections have been obtained in most cases uncer the condition that radiation imprisonment cannot be neglected and corrections are applied accordingly. The values of quenching cross sections depend on the correction factors and are probably accurate to within 50°, ‘The various processes associated with quenching of Hg(P,) and other excited atoms have been studied extensively and are discussed in the following sections, IV-2,, MERCURY SENSITIZED REACTIONS, Mercury sensitized reactions are predominantly those involving HxCP,) atoms, Few susie have bean made of Fgl'P,) atom sensitized resetions The Hg(*P,) state lies 4886 eV above the ground state. The lifetime is, Oia ee The Hg) atoms ate produced om absorp of 2597 A light by ground state atoms. The reaction of Hig(*P,) atoms has been studied extensively since the pioneering work of Cario and Franck (188) in 1922 in which they showed that reaction products of Hg(*P,) atoms with Hy are capable of reacting with metallic oxides, indicating the production of atomic hydrogen. Apa rom is intrinsic intrest, HgQ°P,) atom sensitized reactions have been used extensively to generate atoms and radicals and their reactions with various molecules have been studied. Detailed quenching processes of Hg(°P;) atoms have been of interest to matny workers in the past 50 years. The Hg(?P,) sensitized reactions may be represented by ihe following types of reactions, although the extent of each reaction path is still unknown for many molecules. 1. Direct dissociation: HgCP,) + RH Hgl'Sy) RH v.12) 2. Formation of mercury hyride Hg? P,) + RH Hel + R (1v-13) 3. Spin- orbit relaxation: Hgt?P,) + M > Hg@?Po) + M (v-14) 4. Electronic to vibrational energy transfer Ha(*P,) + M+ Hg'Sy) + MP (Iv-15) where M! signifies vibrationally excited molecules 5. Formation of electronically excited molecules, such as HgPP,) + CS, + Hgl'So) + CST (1v-16) where CS$ means electronically excited CS. WA, Mercury Senstized Reactions 145 ‘The extent of processes (1V-12) to (1V-16) depends on individual molecules The quantum yields for these provesses have been estimated for some molecules. Some examples of quenching processes are given below. I-21. HeCP,) + Hy The production of atomic hydrogen by the Hg(>P,) sensitized reaction has been known for many years and the reaction his been used as a clean source oF H atoms. Two processes have been postulated without direct evidence of the primary products HgCP,) + H. > He('S,) + 2H (IV-17), Hg@@P,) + Hy + HeH +H (1V-18) Recently the production of HgH has been shown directly by optical absorp tion in the Hg(°P,) sensitized flash photolysis of Hy by Callear and his coworkers (176, 177, 180). The quantum yield (177) of FigH formation is estimated to be 0.80 $0.1. Other minor processes are also possible HgC'P,) + Hy + Hg Py) + Hy (IV-19) Hg(*P,) + Hy + HgC'S,) + HY (Wv-20) where H} signifies vibrationally excited H The quantum yield of (3P5) production (IV-19) is less than 0.03 (180). Therefore, the most important process must be the formation of HH. This conclusion is in disagreement with that of Yang et al. (1063), who have concluded from phase space theory that the production of vibrationally excited H, is most important. V2.2. HgCPy) + Nas HgCP,) + CO ‘The quenching cross sections for Np, CO, and NO for processes (IV-14) and {IV-15) have been obtained by Horiguchi and Tsuchiya (481) by measuring the steady state concentrations of Hg(*P,) and (3P4) atoms by optical absorption at 4358 and 4047 A, respectively in the presence of quenching gases. The reaction of Hg(?P,) with Nz leads predominantly (481) (>-90"%) to the formation of Hg(*Po) with a quenching cross section of 0.36 « 10" em? while collisions with CO (481) produce Hg(*P,) and ('S,) in a ratio of 35:1 Since Hg(?Po) atoms are predominantly produced from (*P,) in the presence Of Na. the reaction of Hg(*Po) with foreign gases M can be studied in Hg Na-M mixtures, The quenching rates for Hg) atoms ate in general much faster than those for (?P,) atoms (180). Vibrationally excited CO up torr" = 9 has been observed in infrared emission of CO (408, 557)1V-2.3. Hg@P,) + H,0; Hg@P,) + NH, More than 50% production of Hg(?Po) was observed in the reaction of Hg(°P,)atoms with H,O and NH, (180), Charge-transfer complexes between the molecules and Hg(?Po) are assumed responsible for continuous emissions near 2900 and 3500 A for HO and NH, respectively [Freeman ea (373, 736)]. m= a . 1V-2.4. Hg(*P,) + Paraffins The main reactions of Hg(*P,) atoms with saturated hydrocarbons are the production of H atoms and alkyl radicals (R) (256): Hg@P,) + RH Hg('So) +R +H ava Substantial production of Ha(?P5) atoms has been seen by Callear and McGurk (180). Continuous emissions that presumably originate from loose complexes between the Hg(*Po) atoms and the hydrocarbons have been observed near 2537 A (938), No HgH has been detected from the (?P,) atom reactions with saturated hydrocarbons (177) Ive HeCP,) + Olefins The primary products of the Hg(*P,) atom sensitized reaction with olefins are electronically excited molecules. For ethylene the process is the production of electronically excited ethylene, C,Ht, probably in the triplet state a°B,, at about 3.56 eV (16). Hg@P,) + CaMg + Hg('Sp) + CHt (v.22) ‘The excited C,H, further decomposes or is quenched by C;H,. Quench- ing cross sections of Hg(*P,) atoms by olefins are usually much larger than those by paraffins (256), Primary products and yields for some quenching reactions are given in Table IV-1 IV-2.6. Hg("P,) Sensitized Reactions The Hg("P,) state lies 6.703 eV above the ground state and has a lifetime of 1.31 nsec. The production of Hg('P,) atoms is achieved by absorption of 1849 A light by ground state atoms. Only a few data are available on the reaction of Hg('P,) atoms and no reliable values have been obtained for quenching cross sections. Relative cross sections for 12 gases were obtained from Stern-Volmer plots by Granzow et al. (418). Quenching cross sections for Hg('P,) atoms are not as widely different from one gas to another as those for Hg(*P,) atoms. Emission at 2537 A was observed when mixtures of Hg and Nz were irradiated with the 1849 A line [Gover and 1-4, Other Atom Sensitized Reactions \S7 Bryant (414), Granzow et al, (417)]. The formation of N3(A*Z) as an intermediate was postulated (417) as Hg(*P,) + Nz + Hg(S) + N(A°E) Ng(A°E) + Hg('So) > Na + He(?P1) Hg(?P,) -+ Hg(?Sq) + hv (2537 A) IV-3. OTHER ATOM SENSITIZED REACTIONS IV-3.1, CAC), 'P,) Sensitized Reactions The Cd(?P,) and (#P,) states are 3.80 and 5.417 eV above the ground state, respectively. The lifetimes are 2.5 psec and 1.98 nsec for (P,) and (Py) atoms (21), respectively. The Ca(*P,) and (1P,) states are produced from the ground state by absorption of the 3261 and 2288 A lines, respectively. ‘The reactions of Cd(*P,) and (*P,) atoms with H,Nz, CH, and NH have been studied by Breckenridge and Callear (145) and Morten et al. (719, 720) Band emission due to a Cd(?Po)-NH, complex has been observed by Morten et al. (719) and similar bands with water, alcohols, and ethers have been observed by Yamamoto et al. (1058). IV-3.2. H@P) Sensitized Reactions The H(?P) state is energetic by 10.2 eV with respect to the ground state and it has a lifetime of 1.60 nsec (32). The HCP) state can be produced by it- radiating flowing ground state H atoms with the 1216 A resonance line, where the ground state atoms are made in a microwave discharge. ‘The quenching of H(2P) atoms by small molecules has been studied extensively by Phillips et al, (1021-1023) and by Tanaka et al. (583, 960). The quenching rate constant ranges from 10~* [Shukla et al. (874)] to 107"? [Wauchop etal, (1023)]em? molec” ! sec~' both for N, and Oz. The discrepancy is partially duc to resonance trapping of the 1216 A line in the optically thick system, In the optically thin system the value is about 107° cm? molec” ' sec~* [Braun et al. (142)]. The reaction of H(2P) atoms with H appears to produce three ground state H atoms [Van Volkenburgh et al {992)]. The reactions of H(?P) atoms with O, and Np yielded electronically excited OH and NH [Wauchop and Phillips (1022)}, respectively. 1V-3.3, Na(?P) Sensitized Reacti ‘The Na(?P) state is 2.10 eV above the ground state (7S). The lifetime of the EP) state is 159 nsec. The Na(?P,2) and (?P 2) states emit $890 and 5896 A14 Production and Quenching of Electronically Exeited Atoms resonance lines, respectively. The Na(?P) states can be generated from ground state atoms by absorption of the resonance lines or by photodissaciation (4 = 1900-2500 A) of Nal (332, 441). The quenching of Na(2P) atoms by Ny yields vibrationally excited molecules with a rate more than the gas kinetic Fate (359). The quenching of Na(?P) atoms by H, also gives rise to vibrationally excited H, [Lee et al. (623)]. The quenching cross sections are dependent both on the translational energy of Na(?P) atoms and temperature. It decreases at higher temperatures (632) and at larger translational energies. Quenching cross sections by inert gases are in general much smaller than those by diatomic molecules (359). Quenching of Na(?P) by CO and (Og has also been studied (359, 633). IV-3.4. Ar(P,,'P,) Sensitized Reactions The Ar(@P,, 'P;) levels are 11,623 and 11.827 eV, respectively, above the ground (*S) level. The lifetimes are 84 and 20 nsec (33), respectively. The Ar(P,,'P,) states are formed by absorption of the Ar resorance lines at 1067 and 1048 A. In the 1 to 100 mtorr concentration range the lifetime of Ar@P,,'P,) atoms is of the order of 10 psce [Hurst et al. (494)], which is 1000 times as long as that of isolated atoms because of imprisonment of resonance radiation. Ifthe ionization potential of molecule i below 11.6 eV, it is possible to increase the photoionization yield (sensitize) by adding Ar to the sample, The increase of the ionization yield is caused by collisional energy transfer between Ar(P,,'P;) atoms and the molecule before the excited atoms return to the ground state by resonance emission. Yoshida 1d Tanaka (1065) have found such an increase in the Ar propane, and ‘ammonia mixtures when they are excited by an Ar resonance lamp. et al. (123) have measured quenching rate constants for Ar(*P,) atoms by Nz, Oz, NO, CO, and H. They are on the order of the gas kinetic collision rate, I-35. Kr(°P,,'P,) Sensitized Reactions ‘The Kr(P,) and Kr('P,) levels lie 10.032 and 10.643 eV, respectively. above the ground level. The lifetimes are 3.7 and 3.2 nsec, respectively (424). The Kr('P,) and Kr(?P,) states are produced by absorption of the resonance lines at 1236 and 1165 A, respectively. Sensitized reactions of Ny and CO by KiPP,,"P,) atoms have been studied by Groth et al. (427), 1V-3.6. Xe(*P,) Sensitized Reactions The Xe(*P,) state is 8.436 eV above the ground (18) state and has a lifetime 6 3.7 nsee [Wilkinson (1043)]. The Xe(*P,) state is produced by absorption 1-4. Reactions of Metastable O Atoms 149 ‘ofthe 1470 A resonance line. The reaction of Xe(?P,) with CO yields various triplet states of COA, e°E, aE), as well as the CO(AH) state, and emission bands from these states have been observed by Slanger and Black (898, 899). OF the total singlet (111) plus triplet emissions 60 + 15% is from the A'TT state, On the other hand, direct excitation of CO by the 1470 A line produces only the CO(dA, v = 7) state (898). Thus, Xe sensitized reaction produces various triplet states indiscriminately. The initially formed collision complex XeCO* has been found to have a lifetime of 25 + 6 psec before it dissociates to give CO* [Freeman and Phillips (374)}. The quenching of Xe(3P,) atoms by H has been found by Shimokoshi to produce H atoms (873). VonBunau hhindler (997) have shown that Xe(2P,), as well as KrOP,), atoms sensitize an exchange between H, and Dy. The photolysis of methane (881), ethane, and propane (996) sensitized by Xe(?P,) and Kr(*P,) atoms has been studied. The detailed mechanism of photosensitiza- tion is complicated since XeP,) or Xef (electronically excited molecule) may be formed at higher Xe pressures. Direct photolysis of molecules may partially occur by the imprisoned resonance lines id 1-4. REACTIONS OF METASTABLE 0 ATOMS AV-4.1. O('D) Atoms The electronic energy of O('D) is 1.967 eV above the ground state. The transition to the ground state O(2P) is forbidden by electric dipole and spin. The lifetime is 150 sec (32). The O('D) production can be detected either by the emission (398) at 6300 A [O('D) + OCP)} of by the absorption at 1152 A [2p 3y' ('D") = 2p" ('D)] (456) [Heidner et al. (455), Heidner and Husain (457, 458)] Photochemical Production of OU'D) Atoms. The production of OCD) atoms has been observed in the photolysis of 0, NOz, Os, CO}, atid NjO 0,500?) + 0D) <1750A NO, SNO + O('D) < 2440.4 0, 80,0.) + OCD) <3100A co, "SCO + O('D) <1670 A, N,0 SN, + OU'D) <3400 A, Physical and Chemical Quenching of OUD) Atoms. Although the direct detection of O("D) has been made only recently, it has been known that 0 atoms produced from the photolysis of N,O at 1849 A react rapidly with N,0 to form N, and NO, while OPP) atoms do not react with NO (794, 864). Furthermore, it has’ been known that atoms produced from the150. Production and Quenching of Electronically Excited Atoms photolysis of NO at 1849 A, NO, at 2288 A, and CO, at 1470 A exchange with O atoms in CO, (73, 815, 1060), indicating the formation of an inter mediate complex CO, which dissociates into CO, + O(°P) in 10-"! to 10°! sec (227). An exchange of O atoms with those in CO, does not take place for the ground state O(?P) atoms. ‘The production of O(!D) atoms is also evidenced by the formation of neopentanol in the photolysis of N,O-neopentane mixtures at 2138 A. On the other hand, OP) atoms react with I-butene to yield 1,2~butene oxide [Paraskevopoulos and Cvetanovié (791)} The reactive O atoms produced from N,O at 1849 A can either be O('S) or O('D), However, © atoms produced from the photolysis of NO; at 2288 A, where the production of only O('D) is energetically possible, show the same chemical reactivity as those from N,O at 1849 A (815, 1060). The results indicate that reactive O atoms must be O('D). Quenching rates of O(!D) with Xe, O3, Os, CO, COz, Nz, NO, N20. Og, Hz, HO, and CH, have been measured (10, 262). Rate constants are on the order of 10~'® em? molec”! sec”, that is, the reactions proceed with almost unit collision efficiency. Noxon (745) and Clark and Noxon (216) have measured the absolute emission intensity at 6300 A in the steady state photolysis of O, and CO, at 1470 A. From the rate of production of O('D) Noxon was able to obtain arateconstant of6 x 10”! cm? molec™! sec“! for O(!D) quenching by O,. Gilpin et al. (398) were the first to detect O(’D) atoms directly and measure their decay following the flash photolysis of O, in the Hartley band. The 6300 A emission disappeared within 200 ysec after the flash at an O, pressure of 3 mtorr. From the exponential decay curve integrated over 600 shots, the authors have obtained a rate constant of 25 4 1 x 10°! cm? molec” sec”! for the reaction O('D) + Oy. Rate constants of O('D) atoms with various atmospheric gases have been obtained also by measuring the decay of O{'D) afier the flash photolysis of O, in the presence of atmospheric gases (455, 456) The decay of O("D} was monitored by optical absorption at 1152 A. It has been found (791) that while N, [DeMore and Raper (274)], Xe, CO, and CO, merely deactivate O(°D) to OCP) atoms, Ilz and Cll Feact with OCD) atoms to form respective products. Overend et al. (787) have found little effect of excess kinetic energy of O(!D) atoms on reaction rates. Reactions of O('D) Atoms with Hz, Oz, NzO, HzO, CHy, and Chloro- ‘fluoromethanes, OUD) + Hy (276). No physical quenching was found (791), DeMore (276) has studied the photolysis at 2537 A of mixtures of Os-H, dissolved in liquid argon at 87°K, The quantum yield of ozone decomposi- 1V-4, Resetons of Metastable O Atoms 1S1 tion is near unity when O, is added to the mixtures, while without O; at least 250, molecules per H atom are dissociated. DeMore proposed that processes with Oy added are Ol'D) +H, +H+OH = kz, =2.9 x 10° ‘cm? molec”! sec™* (1V-23), H+0,%HO, (1V-23a) “The OH and HO, radicals produced do not react further with Os. Hence, the quantum yield of O decomposition is near unity Gn the other hand, without Oy the mechanism is (IV-23) followed by chain reactions H +O; OH" + 0; OH! + 0,-+H +20, (v.23) (1-230) where OH! indicates vibrationally excited OH (v" up to 9}. ‘O('D) + O; (392, 918, 1068). The reaction to form O,('E) was first suggested by Young and Black (1068) O('D) +O, + OFP) + OE) yg = 7 107"! em? molec” sec” (v.24) “They observed the O,("E) emission band at 7620A by the steady state photolysis of O, at 1470 A. In the photolysis of 0-O2 mixtures at 2537 A ina flow system, Snelling and Gauthier (918) and Snelfing (919) have found that the yield of ©,('E) production is 85 + 15%. O('D) + N,O (794, 816, 864). The reactions of O('D) atoms with N,0 are O('D) + Nz0 +N, + O2 kas (1V-25) O('D) + N,0 - 2NO Kae (1V-26) with a 1:1 ratio, while OCP) atoms do net react with NzO. The reaction is fast with a value of 2 x 107! cm? molec”! see“! for kys + kre O('D) + HO. The flash photolysis of Os-H,O mixtures in the near ultraviolet yields OH radicals [Engleman (335), Biedenkapp et al. (109)}. 0,5 OUD) + Ox") O('D) + H,0 +204 (v.29, Paraskevopoulos and Cvetanovié (793) have studied the photolysis of N,O-neopentane-H,O mixtures at 2139 A, They have obtained the reaction rate of O('D) with HO relative to that with neopentane, The deactivation of O('D) to (°P) by HzO was examined by adding I-butene to N;O-neopentane-H,O mixtures. No products characteristic of OCP)152. Production and Quenching of Electronically Excited Atoms addition to I-butene were found, The process O('D) + HzO 20H kay = 3.5 x 10°" em molec”! see“! (LV-27a) must be predominant (>90",) (888). It has been observed that hydroxyl radicals formed are vibrationally excited up to v” = 2 (335). The newly formed OH bond acquires most of the available energy while the other OH bond remains vibrationally cold (335). The rexction of OCP) atoms with 1,0, however, does not form OH (312). O('D) + CH, (312, 856), The forma fash photolysis of NzO-CHy mixtur. reaction jon of OH radicals is found in the indicating the occurrence of the OUD) + CHy>OH + CH, — kyy=4 x 107! em! melee! see"! (lv-28) No physical quenching of O("D) to OCP) was found (791). Greenberg and Heicklen (420) have estimated the OH production yield to be 95", of the total. Lin and DeMore (636) have concluded the reaction Ol'D) + CH, + Hy + CHO (v.29) occurs to an extent of 9% O('D) + Chiorofluoromethanes. The reactions of O('D) with chioro- Nuoromethanes have been studied by Donovan et al. (316), Gillespie and Donovan (396), and Fletcher and Husain (362), The reactions yield predominantly CIO radicals 01D) + CECI, + CFCI,_, + COW?) (1-294) The rate constants are large (~S x 10°" em molec” see” OUD) Atom in the Upper Atmosphere. The presence of (4D) atoms in the upper atmosphere has been recognized by the observation of the air low emission at 6300 A. The formation of O('D) atoms must be due to the photolysis of O, by light of wavelengths below 1750 A (> 100 km) and to the photolysis of O, in the Hartley band (< 100 km). The reaction O('D) +O may produce O,('E) in the stratosphere (918, 1085). Reaction rates and products of O('D) with various gases are given in le IV -2. 1-42, O'S) Atoms The electronic energy of O('S) atoms is 4.189 eV above the round state. The transitions of O('S) to the ground and to the O('D) statesare forbidden. IW-4. Reactions of Metastable © Atoms 153 able 1V-2. Reaction Rates and Products of OCD) with Various Gases ate Constant Products" (10° "em? mace" see" Ret Xe Xe OUP) Lat 03 1 ON O's!) + OCP) O75 015 Mx, 610, 745, 918 [OeE. 1+ 008) 108, 545, 106% Nee Ocry 058 4015 1 My < 10°" 556,883 NEO So co O44 OrR) 075 £015 31791 Cots OF) soe No [No + OVP) Rend 0 n son 29405 276.791 on 0, + Ota or XE) $0425 392, 458, 1027 2040; co, Co, + bury tx403 313,791 NO Ne Os] 22408 xo 2N0 No, (NO + On) 2s 0s 0 1,0, 2011 35406 335, 458, Bhi ony Ons cH, 40407 312.646, 791 Hy + CHO. 275,420 neoCMy; Nespentanol wg42a os * indicates a vibrationally excited molecule Ret 1012 The lifetime of O1'S) is about 0.71 see (32). The O('S) state ean be identified by the emission at 5577 A [O('S) + O('D)] oF by the absorption at 1218 A VCP) = 2yCS)] [yee MeConkey and Kernahan (673)] Photochemical Production. The formation of O('S) atoms has been ‘observed in the photolysis of ©}, NO. tnd CO; 0,8 00P)+ 01's) <1332A N,05N, + O'S) < 215A co, $c0 + 0l's) <1286 A Reactions of O'S) Atams. In spite of the higher clectronie energy of O'S) than of O('D) the quenching rate constant of the former atoms by many gases iy in general much smaller than that of the latter atoms Table IV 3 shows some results obtained mainly by Welge et al. (48, 349, 646, 949, 1035). A mechanism to explain a large difference in physicalfo4 rroauciion and Quenening of Lietromeaily kxcited Atoms Table 1V-3. Comparison of Quenching Rate Constants of O('D) and OCS) Atoms, at Room Temperature (10, 646) (em? molec“! 06") OCD) 00's) Xe 14 10-184 N 055 x 10-1" CO 075% 10717 Oo; 078 x 1071" Hy 2910 23 19-1 CO, Rx 10° 3.7.x 0 Oy Sxl Ska WO + Physical quenching of O(D) 0 OP * Chemical quenching, quenching has been proposed by Donovan and Husain (310) and by Fisher and Bauer (360). The observed quenching properties of O('S) and O("D) by Nz, for example, may be explained by a correlation diagram show in Fig, IV-1 in which C, symmetry is assumed for the O-N, collision complex. From Table 11-4 it can be shown that three reaction surfaces (34° + 24") are available for O(?P) + Nz, five surfaces (344° + 2'4”) are available for OUD) + Nz, and only one surface (14’) correlates with OCS) + Nz. Quench- ing of O('S) by Nz is probably physical, since an O(!S) + Ny surface does not correlate with NO + N(*S) surfaces. Physical quenching of O('S) would involve a high energy barrier (10° collisions are necessary for quenching). On the other hand, O('D) quenching would proceed with the initial formation of highly vibrationally excited ground state N,O and its subsequent dissociation into O(?P) +Nz by nonadiabatic crossing from "A" to 74’+ 3A” surfaces, The reaction O('D) + Nz» NO + N does not ‘occur since it is highly endothermic. A similar trend has been observed for quenching of $('S) and S(°D) by noble gases. I is not known whether quenching of O('5) by O, is physical or chemical. It is likely that the products would be 20; or O, + 20, since the rate constant is very large in this case. Intensity Enhancement of the O('S)—+ O('D) Transition. Kt has. been found by Filseth et al. (349) and by Hampson and Okabe (436) that gases such as Hz, No, Ar, Kr, and Xe enhance the O('S)-» O('D) emission intensity. This enhancement has been attributed to the shortened lifetime of the I-A, Reactions of Metastable O Atoms 15S the reactions © + Ns and NO +N. C, symmetry late, Three reaction paths are availabe for O('P) + Nasfive for OCD) + Ng, and ane for O(1S) + Ny. Quenching of (5) by Nas probably physical and would require a high energy barrie, while quenching of O(*B) to O("P) ted by nonadlabaticerosing trom 14" to "4’ + 294” surfaces, Reprinted with permission from Doaovan and Husala, Chem. Rer., 70, 489 (1970). Copytight by the ‘American Chemieal Society. emission. It has been known that the atomic emission line at 5577 A is accompanied by diffuse bands towards shorter wavelengths in the presence of Ar (240), Nz (238), and Xe (254). A proposed mechanism by Hampson and (Okabe (436) is that while the atomic transition is forbidden by the selection rules, AJ =0, £1, it becomes allowed as a result of the loosely bound molecular formation M—O('D;) (M, an added gas). The transition is now allowed since M—O('D,) has components © = 2, 1, Qalong the internuclear axis, and the selection rules are AQ = 0, = 1.186 Production and Quenching of Electronically Excited Atoms The intensity of the collision induced emission follows the order Xe > Ke> Ar> N > Hz > He (349, 436), According to Cunningham and Clark (254) this molecular emission is 40°, of the total quenching process in the ease of Xe, but it is only 1% in the case of Ar. From the Stern-Volmer type plot of the intensity ratio of /, (with added gas) to 19 (without added ‘against the pressure of an added gas, Black etal. (115) have recently o! the rate constant for induced emission by He, Ar, Ny. H,, Kr,and Xe. O'S) in the Upper Atmosphere. The presence of O('S) in the upper atmosphere is indicated by the emission line at 5577 A in the airgiow and aurora. The mechanism of formation and destruction of O('S) atoms tycen of great interest in aeronomy. Zipf (1085) gives a detailed account of various processes of O('S) in the upper atmosphere. IV-S, REACTIONS OF METASTABLE $ ATOMS IV-8.1, S(1D) Atoms ‘The S(*D) state lies 1.145 eV above the ground S(°P) state and is metastable with a lifetime of 28 sec. The S('D) state can be detected by absorption in the vacuum ultraviolet at 1667 or 1448 A (33). However, in spite of much effort S("D) atoms have not been detected by optical absorption in the vacuum ultraviolet flash photolysis of OCS because of a rapid reaction of S{'D) with OCS S('D) + OCS +S,(a'A) + CO The appearance of absorption bands near 1900 A, due to the transition Sxy'd, + a'A,) indicates S('D) atoms are formed in the primary process since S(°P) atom reaction with OCS yields S(X?E, ) rather than 8,(a'A) [Donovan (305)]. The ultraviolet photolysis of OCS is a convenient source of SUD) atoms [Gunning and Strausz.(430)]. The S('D) atoms react with parallins to produce the corresponding mercaptans, while S(°P) atoms do hot react with paraflins, Thus, the production of mercaptans may he used as diagnosis for S{'D) atom formation, The reaction of SP) with ethylene yields only ethylene episulfide [(CH2)2S]. while S("D) atoms form ethylene spisulfide and vinyl mercaptan (430). Donovan et al. (308) have found high quenching efficiencies of S('D) atoms by inert gases. Quenching efficiencies for S{"D) are much higher than those for S(!5) atoms. The analogous trend has been found for O('D) and O('S) atom quenching efficiencies. They have explained the higher quenching efficiency of S('D) atoms by Xe on the basis, of crossings of the potentiat energy curves for Xe -$("D) and Xe--S('S) molecules, respectively, with that for a Xe~S(*P) molecule. Quenching rates of S('D) by atoms and molecules have been measured by Little et al. (642). 1-6, Reactions of Metastable and Ground State C Atoms 4ST Ws S(1S) Atoms The S(S) state lies 2.750 eV above the ground state. The S('S) state is metastable with a lifetime of 0.47 sec (33). The S('S) atoms can be detected by absorption at 1687 or 1782 A. The emission at 7725 A ('S —'D) or at 4589 A('S + "P) may also be used to follow the reaction rate of S('S) atoms. The photolysis of OCS in the vacuum ultraviolet produces S('S) atoms [Dunn et al. (326) Donovan et al. (305, 308)]. Quenching of S'S) by various ‘atoms and molecules has been studied by Donovan et al, (308) and by Dunn et al (326). Quenching rates by NO and NO, are extremely fast and may involve chemical reaction (326). Neither the products specific to S(*S) atom, reactions nor the extent of physical quenching is known. Quenching rate constants of S('S) are in general much less than those of S('D), just like for O atoms. Collisionally induced emission S('S)—+S('D) has been found to be a ‘major path for deactivation of S(!S) atoms by rare gases and by N, [Black et al. (116)] in analogy with O('S) atoms described in Section IV-42. REACTIONS OF METASTABLE AND GROUND. STATE C ATOMS 1. CED) Atoms, The C('D) state is 1.263 eV above the ground state C(?P) and has a lifetime of 53 min (32), The generation of C('D) atoms is achieved by the photolysis ‘of carbon suboxide in the vacuum ultraviolet. The concentration of C("D) atoms can be monitored by optical absorption at 1931 or 1482 A [Braun et al, (141), Husain and Kirsch (500)], Quenching of C('D) atoms by noble gases (499), diatomic molecules, and polyatomic molecules has been studied by Braun et al. (141) and Husain and Kirsch, (498-500). Reactions of C('D) atoms with molecules are, in general, fast (collision eliciencies of 0.1 to 1). 1V-6.2. CC'S) Atoms The C('S) state lies 2.683 eV above the ground state CP) with a lifetime of 2 sec (32). The production of C('S) atoms is observed in the photolysis of carbon suboxide in the vacuum ultraviolet, The C{'S) atom production can be detected by absorption at 2479 or 1752. Rate constants of Cl'S) with molecules have been measured by Meaburn and Perner (687), Husain and Kirsch (505), and Braun et al (141). The rate constants are in general much smaller (collision efficiencies 10°? to 107%) than those for C('D), in analogy with the results for O("D) and O('S) atom quenching rates given in Table 1V-3.188 Production and Quenching of Electronically Excited Atoms ‘The difference in reactivity of C(*D) from C('S) is explained by Donovan ‘and Husain (310) on the basis of symmetry correlations between reactants (for example, carbon atom and hydrogen molecule) and products (methylidyne and atomic hydrogen). Figure IV-2 shows the correlation of C + Hy with CH +H. The reaction C+ H, is assumed to form CH, of C, symmetry (or C, symmetry), which dissociates subsequently into CH +H. Correla- omcctsty+ cncetsy+H cncater C101 + Me, onotny +H 4 cP + He A °. ong x79) Fig, 1V-2. Symmetry correlations between C + H and CH + H. The formation of CH, in C, symmetry (or C;,) is assumed. The reaction C('D) + H, proceeds through *° and 44” to form CH(XT1) + H with high eficiency. On the other hand, CC'S) + Hy correlates with highly excited CH + HT and the reaction requires a high activation energy. ‘The C('S) atoms are probably deactivated to C('D). CCP) + Hy forms CH,(X°E, ). Reprinted with permission from R. J. Donovan and D. Husain, Chem Rev. 70,489 (1970) Copyright by the American Chemical Society. IVT. Reaations of Other Metastable Atoms 189 tions of species C('P,"D,'5) + Hy with those of CH, in C, are given in ‘Table 11-4, Correlations of species of CH, in C, with those of CHCTI. 2A, 2E-,25*) +H are given in Table I-3, The species CP) +H, becomes 34’ +234" in C,, Two of them 4’ +24") correlate with CH(X?T) + 11 and the third species, 74”, becomes CH(4#A) +H. At low kinetic energy of CP) (<1 eV), CH, is the product. For species C(!D) + Hy five surfaces GIA‘ +214") are available, wo of which (14 +'A") correlate with CH(X?T1) + H and another two (14’ + '4”)are associated with CH(47A) + H. The last one ('47) becomes CH(C?E*) +H. The production of CH(X?11) + H is fast and requires no activation energy. On the other hand. the species C('S) +H, has only one surface (‘4’) that correlates. with highly excited CH + H. The reaction needs at least an activation energy of 25 eV and C('S) atoms are more likely to be deactivated to C('D) atoms. 1V-6.3. CCP) Atoms The ground state C atoms are produced by the photolysis of carbon suboxide They can be monitored by optical absorption at 1657 A. Reactions of CCP) atoms with molecules have been studied by Husain and Kirsch (497,498) and Braun etal. (141) IV-7. REACTIONS OF OTHER METASTABLE ATOMS IV-7.1, N@D,7P) Atoms The N(?D) and N(?P) levels are 2.38 and 3.576 eV, respectively, above the ground level (45) and are metastable with ‘ifetimes of about 17 hr and 12 sec. respectively (32). The N(2D) atoms can be detected by absorption at 1243 and 1493 A and N(?P) at 1412 and 1744 A. In emission the 5199 A line is due to the transition 2D +S and the 3466 and 10,400 A lines are from the transitions ?P -» S, and #P — *D, respectively. The ND, P) atoms can be produced from the photolysis of N,O in the vacuum ultraviolet. Quenching rates of N(?D) and (7P) atoms by Ha, Nz, Oz, CO2, and NO have been measured by Husain et al (506) by time-resolved attenuation of absorption at 1493 and 1744 A, respectively. The quenching of ND) atoms by NO appears to be chemical reaction to produce NO(B'T1) + N2 N@2) + N,O—» NO(?M) + Ny (v.30) Quenching of NED, *P) by O2, NO, COs, NO, Nz, H.O, Ar, and He hhas also been studied by Lin and Kaufman (635) and by Slanger and Black (908) Atmospheric Reactions, The presence of N(7D) atoms in the upper atmosphere has been known from the 5290 A emission line observed in the160 Production and Quenching of Electronically Excited Atoms sper atmosphere. The reaction of N(2D) atoms with O; is believed to be a source of NO NUD) +O, + NO + OCP) (v3) 1V-7.2, Br@Py,) Atoms The Br(?Pj,2) state lies 0.456 eV above the ground *Ps,z state and is meta- Mable with a lifetime of 1.12 sec. The Br(?P,,2) atoms can be detected by absorption at 1532, 1582, and 1634 A. The flash photolysis in the vacuum Ultraviolet of HBr, Bry CHCIBr, and CF,Br has producd Bri?Py,2) titoms that have been observed by optical absorption [Donovan and Husain (299)}- The quenching ellicieney of Br(?P,,) produced from the ash photolysis of CFBr by various gases has been studied by Donovan and Husain (300) I-73. 1G Py) Atoms The IP a) state is 0.942 eV above the ground state *P,2 and is metastable with 3 I ime of about 0.05 sec [Husain and Wiesenfeld (495, 496)]. The IEP, 3) atoms can be detected cither by optical absorption at 1844, 1799, and 2062 A or by emission at 13152 A. The 17P,,2) atom production was Gbserved in the flash photolysis of CF,1 above 2000 A [Husain and Wiesenfeld (496)}. The flash photolysis of HT above 2000 A has produced 12Py,.) and I(2P5,2) with a ratio of 1:5 [Donovan and Husain (297)]}. Phys- ical quenching rates of 1(2P,,.) atoms by diatomic and polyatomic molecules have been measured by Husain et al, (269, 448, 496) und, Donovan et al, (298, 303). Quenching efficiencies range from 10™* to 10"*. The low {quenching efficiency by CFyI favors the detection of 17,1) atoms. The quenching by HI, HO, O;, NO, and 1, has been found by Donovan and Husain (298) to be eflicient. The quenching by Cl, Br2,1Clyand [Br has been sitributed by Donovan et al, (301) to chemical quenching, On the other hand the quenching of IP, 2) by alkyl iodides (RI) is primarily physical, although the reaction to form 1, + R is exothermic (303). The quenching efficiencies are on the order of 10"? to 102. The fraction of 1(?Py,2) produetion from inC HI photolysis is twice as much as that from i-C Hy I-74, AsCD,,?P,) Atoms The As(2Dy,2) and As(2Ds)3) states are 1.313 and 1.353 eV, respectively above the ground (48) state, The As?P,,2) and As?P,.) are 2.254 and 2312 eV, respectively, above the ground state. The AstD,) and ASU P,) ‘toms are generated by the photolysis of As(CHs)s and AsCl,, respectively (105, 172) IVI. Reactions of Other Metastable Atoms 161 IV-7.5. Sa('D, 1S) Atoms The Sn(*D) and Sn('S) states are 1.068 and 2.128 eV, respectively, above the ground (*P,) state, The Sa(*D) and Sn(S) atoms are generated by the photolysis of Sa(CH,), and SnCla, respectively. (151, 152) 1V-1.6. Pb('D, '$) Atoms The Pb('D) and Pbi'S) states are 2.660 and 3.653 eV above the ground state, respectively. The Pb(*D) and (1S) atoms are generated by the pulsed photolysis of lead tetraethyl, The quenching of the Pb("D) and ('S) atoms by various molecules has been studied by Husain and Littler. (501, 503, 504)chapter V Photochemistry of Diatomic Molecules V-1, HYDROGEN ‘The ground state of Hy is X*E,. Dol H—H) = 4.4780 eV (Ref. 468) Absorption starts at 1108, The banded absorption region 850 to 1108 A corresponds to the transition B'E—X'E} (Lyman bands). The dissociation limit at 844.7 A corresponds to H, Hs) + HQp,2s) (vet) Below 844.7 A the banded structure (D'T1,~X'E,)) is superimposed on a continuum [Mentall and Gentieu (695)]. The absorption coefficients in the region 700 to 860 A have been measured by Mentall and Gentieu (695). V-2. HYDROGEN HALIDES V-2.1. Hydrogen Fluoride The ground state is X'E*. Dol H—F) = 5.86 + 0.02 eV (286a). Absorption starts at 1613 A. The absorption coefficients of a weak continuum below 1613 A are given in Fig. V-1 V-2.2. Hydrogen Chloride ‘The ground state is X'Z*, DoH—Cl) = 4.431 + 0.002 eV (24). The absorption coefficients of the continuous region 1380 to 2000 A are given in Fig ‘V2, and those in the region 1050 to 2100 A are given in Fig. V-3. Photolysis at 1849 A produces H atoms with about 2.27 eV excess kinetic energy. The primary process is most likely the production of H+ Cl with a quantum yield of unity since the absorption is continuous, The Cl atoms are in the #P,j, state (Mulliken (725)}. The photochemical reactions expected are similar to those of HI [Wilson and Armstrong (1051)]} HLH + ClePy,2) (v2) H+HCI+H,+Cl (V-3) Cl+Cl+M-—Cl, +M (V-4) ou aoe Fig. V-1. Absorption coeficient of HP. € is in unks mot cm" base 10 (at_room woo ure). From Safary et al (849), re 1800 by permission. Copyright 1981 by the A ‘American Institute of Physies. ° Fig. V-2, Absorption coeficient of HCL. & isin 2000 | woo | ano unitsof atm Yase 10 a room temperature From J. Romand and B, Vodar (840), reprinted by A permission of the Academie des Sciences. A ross sections of HCI in the region 1050 to 2100 A. ais in units of, ‘oom temperature, From Myer and Samson (727), reprinted by permission’ Copyright 1970 by the American Institute of Physics. 163Wot Photochemistry of Diatomic Molecules 500. Fig. V-4. Absorption coeficient of HBr. € is in is of mol~ em”, base [Oat room t Reprinted with permission from B. J. Hucbert and WOO" 2000 2400 RM. Martin, 4. Phys. Chem. 72, 3046 (1968). A Copyright by the American Chemical Society. V-2.3. Hydrogen Bromide The ground state is X'E*, DoH --Br) = 3.750 + 0.01 eV (24), Absorption starts at about 2500 A and is continuous down to about 1600 A. The absorp. tion coeflicients in this region are given in Fig, V4. The region 1190 to 1380 A contains various discrete transitions ‘The primary photochemical process in the continuous region appears to be the production of the ground state Br atoms *P,,, [Milliken (725)], HBr 3H + Br?P,,,) (v-5) The H atoms have excess kinetic energy, 296 and 1.25 eV at 1849 and 2480 A, respectively. The secondary processes are [Fass (444)} H+ HBr H, + Br (V-6) Br+ Br+M-—+Br,+M (v-7) ‘The photolysis of HBr has been used for an actinometer in the region 800 to 2500 A, as ©, = 1 has been established in comparison with an NyO ‘tctinometer [Martin and Willard (663)} V-2.4. Hydrogen lodide The ground state is X'E", D(H —1) = 3.084 + 0.002 eV. Absorption starts at about 2800 A and is continuous down to 1800 A. The absorption coell, cients in this region are given in Fig. V-5. The upper state must be repulsive 4s shown in Fig. V-6, The quantum yields of H and 1, formation from Hl at 1849 A and at ~ 78°C and 25°C are 1.05 4 0.05 and 13 + 0.3, respectively (Martin and Willard (663)]. The results may be explained by & mechanism HISH 41 (v8) H+HI+H, +1 9) 4M +1, +M (v-10) ‘The excess energy beyond that required to break the HI bend is 3.65 eV. at 1849 A. This excess energy appears primarily as the kinetic energy of H Hydrogen Hades 165 tt 1 (crs) Absorption coeficients of HI and contribution of the transitions tothe absorption continuum in the ultraviolet region. Solid curve, absorption coefficients € of HI in Units of I mot”! cm" base 10 at room temperature, Reprinted with permission from B. J. Huebert and R.M. Martin, J. Phys. Chem, 72, 3046 (1968). Copyright by the ‘American Chemical Society, Dashed curves, absorption coefficients of the transitions M12", N3—!Z*, and 11", The M1, and states dissociate into H+ ICP, hile the "Ily state dissociates into H+. 1@P,,). The arrows indicate four incident wavelengths (2662, 2537, 2281, and 1850 A) at which the ratios of ICPy,2) 10 IP y.) are obtained. (219) reprinted by permission. Copyright 1975 by the ‘American Tost toms, However, ®., both at 1849 and 2537 A is unity, showing little or no enhancement of the yield by hot hydrogen atoms. The production of the metastable *P,,, 1 atoms is energetically possible below 3100 A. At 2790 A Oldershaw ot al, (777) estimate the quantum yield of I(2P,,.) production to be 0.11 + 0.14, Estimates by Compton and Martin (231) for the same yield are 007 + 0.1, 0.19 40.1, and 00 +01, respectively, at 2537, 2288, and 6 wv HR) A — H#UCP A) Fig v6. Potential energy curves of HL. From Wilson and Armstrong (1051). Originally from ‘Mulliken, Phy. Rev. 51, 310 (1937), Reprinted by permission. Copyright 1937 by the American Physi- fal Society100 Photochemistry of Diatomic Molecules 1850 A. Thus, in the region 2800 to 1800 A the ground atom production appears to be predominant. However, Cadman and Polanyi (165) estimate the IPs.) production to be about 0.5 at 2537 A. Clear et al. (219) have found the production of I(?P,,2) to be 0.36 at 2662 A by measuring the translational energy of recoil H atoms produced from HI by a pulsed polarized laser. V-3. CARBON MONOXIDE The ground state of CO is X'E*. Dy(C—O) = 11.09 eV. (24). A weak discrete absorption in the region 1765 to 2155 A corresponds to the Cameron system @®I1-X!E*, In the vacuum ultraviolet absorption bands in the region 1280 to 160A correspond to the fourth positive system A'TI-X"E*, The absorption cross sections of this system are given in Fig, V-7. Since the widths of the CO rotational lines are much smaller than the instrumental resolution (~ 10 em”), it is not possible to obtain the absorption cross section of each rotational line [sce Section I-8 for details]. Thus, the cross sections shown in Fig. V-7 are much less than the true cross sections. An estimate of the integrated absorption coefficient of the (0,0) band is 1.7 x 10cm! atm”! (899). Various electronic states and transitions are given in Fig. V-8 ath positive gaQq (id A 1300 Fig, Y—7.,Absoraton cross sections of CO in the region 10500 1750 A. sin units of ‘em, base ¢, at room temperature. From Myer and Samson (727), resolution, 0.25 A. Reprinted by permission. Copyright 1970 by the American Institute of Physics, V3. Carbon Monoxide 107 er ie —— ol V-8. Energy level diagram of CO: AP, fourth positive; B-A, Angstrom; CoA, Herzberg: B-X, Hopfield. Birge: 1-X, Cameron; d-a, triplet: e~a, Herman ‘6-4, third positive; ema, 3A bands; a’-a, Asundi, The 1470 A line is in coincidence withthe dA (e" = 7) (898). From Gaydon (By. 210, reprinted by permission of ‘Associated Book Publishers 11d. tye V-3.1. Photochemistry Since the dissociation energy of CO is 11.09 eV, the photochemical products formed by absorption of light of wavelengths above 1118 A must be duc to the reaction of the electronically excited CO(A'M1). The photolysis products both at the Xe and Kr lines are CO, and C30; with quantum yields of about 6 x 10°? and 3 x 10°, respectively [Groth et al. (427)}. Since fluorescence quenching takes place with more than unit collision efficiency [Becker and Welge (79)], the excited CO must be deactivated mostly to the ground state, Stanger and Black (906) have concluded that quenching of the aA (v' = 7) state by CO results in vibrationally excited CO with high effciene ‘A proposed mechanism for product formation is (427) 0% cor wany CO* + CO-+CO, +E (v.12) c+co%c,o (v-13) ¢,0 +co4c,o, (v-i4) where CO* signifies the electronically excited CO. It has been concluded by Slanger (898) that by absorption of 1470 A light, CO is excited to d?A (v’ = 7) (see Fig, V-8), since only the emission due to the d'A-«M1 (the triplet bands) has been observed. The 1470 A line is in near coincidence with the transition from XE" (v" = 0,J = 15) to PA =7,J = 14), while the 1470 A line is off by 367 em! from the ional level of the A'TT state in agreement with the observation168 Photochemistry of Diatomic Molecules ‘Table V-1, Electronic States and Lifetimes of CO leteonic State (eV? Lietime AML -KO2TS LO nsec (Ref. 509), 10.5 + I nsec (Ret 466) 16 + I nsec (Ref. 207) dependent on v BIE" 10.776 20sec B's! 411 Am LE £012 x 10" see™! (Ref 716° BIE ANE" A= 40% 10" sec (Ref. 4667" M6009 75 + 1 msec(Ref. 614), 3~ 450 msec (J" dependent) 9.51 +063 msec (Ref. 525), 8.75 msec (average) (Rel. 526) HQ 751926 ysee, (Ref 902) J and 8 dependent e'S—7H990 3 see (Ref. 903) » 10394 $1.64 1.2 nsec (Ref 6464). 97 + 9 nsee (Rel. 716) 526 $0.3 nsce (Ref 910) 0" dependent) From Ref 24 * Transition probability see") that no emission from the A'I occurs. On the other hand, the Xe sensitized Auorescence of CO (79, 898) consists of emissions from the dA, e*E~, and 45", as well as that from the A'TL This indicates that strict resonance of the incident photon energy with a quantum state of the electronically teavited CO is required for direct uorescence while no such restriction is necessary for sensitized fluorescence. Slanger and Black (907) have also observed emission from the eS. state by exciting CO with the 1483 A sulfur line. The transition to this level is facilitated by the perturbation of the nearby A" state. Certain rotational levels of triplet states are perturbed by the A" state and emissions from these levels are seen by excitation of CO with a fourth positive emission lamp [Slanger and Black (900)]. The CO(u'Ml) state is produced by a weak absorption of 2062 A light [Harteck et al. (443)] or by the Hg("P,) sensitized reaction [Liti et al, (644) Simonaitis and Heicklen (885)]. The reaction products of CO(@TH) are CO, and C,O3, which are probably formed by a similar reaction sequence proposed for the photolysis, of CO by Xe and Kr lamps. Quenching rates of COla°F1) by various gases have been measured [Taylor and Setser (963)]. The rate constant is on the order of 10° cm? molec” sec™'. Various electronic states and their Iietimes are given in Table V1 |. NITROGEN The ground state is X'E, and the bond energy, Dy(N-— N), is 9.760 + 0.005 €V (8), corresponding to the incident wavelength 1270 A. The Lyman-Birge- V4. Nitrogen 169 Fig. V-9. Energy level diagram of Ny DAN—N)=9.76eV; LBM, Lyman Birge-Hopficld bands; V-K, Vegard- Kaplan bands: 1, first postive bands: 2°, secind positive bands. From Gaydon (8, P. INK, reprinted by permission of Asso” x's «ated Book Publishers Ld. Hopfield bands (u'T,-X"E,') are the main absorption bands in the region 1000 to 1500 A. The energy level diagram is shown in Fig. V-9. Although the Lyman-Birge-Hopfield bands are the most intense bands in the region above 1000 A, the transition by electric dipole is forbidden and the absorption coefficient is tess than 0.1 (em~ ' atm~')(31). Table V-2 gives absorption coefficients of some of the bands. The absorption becomes prominent only below 1000 A. The spectrum shows a strong banded structure between 660 Table V-2. Absorption Coefticients (31) of Some ‘Lyman-Birge-Hopfield Bands of N, 4 Bad (om tat 0,0 1450 ous 10 1416 009 20 1384 on Xo 1354 007 40 ns 008 30 DW 0x 60 273 009 70 1349 003 Ko 127 02 9.0 120s 002 10.0 1185 002 10 1166 02170. Photochemistry of Diatomie Molecules and 1090 and a continuum below 669A [Cook and Metzger (234)] Tonization takes place below 795.96 A of incident wavelength (17) ve Photodissociation in the Upper Atmosphere Photodissociation of Nz in the region 600 to 1000 A contributes to the production of the metastable (?0*,"P*) and ground state N atoms in the 100 to 300 km region of the carth’s upper atmosphere. Cook et al. (235) suggest that the metastable N atoms are produced mainly from the contin: uous absorption, which amounts up to 28", of the total absorption by Nz (235), Hudson and Carter (487) have observed that most N, absorption bands in the region 800 to 960 A have widths greater than 2cm™?. They suggest that the broadened rotational lines are due to predissociation. Then the production of N atoms in the region 100 to 300 km should be much greater than an estimate based on the production rate from the continuous absorption only. Beyer and Welge (106) found the production of N(*P) (10.3 eV above ground state N atoms) atoms below the incident wavelength, 617 A, corresponding to N, SNP) + NAS) (v-15) The extent of the process is on the order of 1% of the total. The reaction of NED) with Oy appears to be a source of NO in the earth's upper atmosphere (635) N@D) +0; +NO+0 (v-16) Table V-3 gives lifetimes of some electronically excited N;. ‘Table V~ Lifetimes of Some Electronically Excited States of Ns Electronic State wy Lifetime WE! — 6224-204 0.9 see (Ref. 189) 2.5 sec (Fy, Fy slates) (Ref. #68, 469) 1.36 see (F,) (Ref. BOK, 869) BY, 7.3991 psec (Ret 531), aIZ, 8449 0.7 see (Ref. 972) aT, 8589115 4 20 psec (Ref 122), 140 psec (Ref. 470) 170 4 30 sce (Ref. 631) OM, 11.050 Wnsee (Ref. $31), 39.7 nsec (Ref. $35), 27 nsec (Ref 352) (© =0) 40.5 + 1.3 nsec (Ref, 181) (= 1)4464 4 14 nsce (Ref. 181) * Benesch al (5 V-S. Nitric Oxide 171 V-5. NITRIC OXIDE The spectroscopy and photochemistry of NO have been extensively studied in recent years. The results are summarized in recent reviews (454, 817) ‘The ground state is XI. The bond energy DolN—O) is 6.496 eV (175). corresponding to the incident wavelength 1908 A. Absorption by NO begins at about 2300 A. In the region 1350 to 2300 A the absorption spectrum fs composed of many discrete rotational bands. The region 1960 to 2269 A 40] NENT em! 30 ABSORPTION OF NO 5 a 8 3 oo 1800 "700 7300 06 7300 WAVELENGTH A (A) ” A o} Fig. 10. From Maxmo (6) reprinted by permision, Copyright 1953 bythe American Tidatute of Physics (a) Awarptioncoefiints of NO. in the region 1500 to 2300 A, tected so °C. Line ame" cm's base (9) Absorption cafes of NO inthe er 00 1500 A efered CA nuts of ate em" base172 Photochemistry of Diatomic Molecales corresponds to the A711 *~ XE transition (7 bands}, The 1598 to 2063 A region is associated with the B?11-X7¥ transition. Absorption bands in the region 1384 (0 1915 A are due to the transitions to the C?M, D?E*, and FES states, Figure V-10u shows the apparent absorption coelficients of NO in the region 1500 to 2300 A and Fig. V-10b shows those in the region 1100 to 1500 A. Because of the lack of resolution of the monochromator, the absorption coefficient given in Fig. V-10d is a function of the slit width and the pressure of the gas (see Section I-81 for details). The true absorption coellicient may be obtained by computation from the oscillar strength and the assumed widths of the rotational lines. According to the computation by Cieslik and Nicolet (214) the true absorption coefficient of individual able V- ‘Ovcilator Strengths for the NO B. 7,5, and ¢ Band Systems. ‘Oscillator Strength? Hee) Transition Band BANNAN (0,0) 2461-8 Bul.o) 2251-8" B20) 133194 L191—0F 3.0) 4611-6, 531-6" HAO) 1381-5, LOU SH WS.) 264 —$), 24-3 16,0) 462(~5) Bi9.0) 3581) U0) 3624-4) BIZ) 21-4) 013.0)” 2.006 (= 4) APEXT OO) 3.99(— 4, 264(—4y" 711.0) 788(~4) 120) 6730 0) 3.60 OMX 510.0) 2491-4) 5.0) 578( 4) 5120) 2244) DE-NM — 0.0) 25.4(—4) (1.0) 4600-4) 2.0) -33.2(-4) means x 10-* From Ref. 103 unless otherwise noted « IK8O 039 1880714 OR-09 0) BL 310 16 at 0 044 wa $s a3 AE cn DEW No MO 6, Mh MO NY CE BT Qo 022102052 BOON 1743 O41 F009 * Quenching haf pressure is equal to (hye)! where ys the rate constant for quenching reaction and cis the mean Ifetime (radiative wnd predisociative) of excited NO. Ref. 693, “Ar quences the CT («= 0). “Ny Induces the transitions D+ A, C-+A by the formation of Ny(AE) (169, 171,175 “At induces the transition D - C with unit efficiency (174. P Reh AIT + Ref. 698 ‘Table V-7. Predissociation of Electronically Excited NC ° aa) 1880 [No emission appears above ind ented levels [(9, P. 197] "Dituocation takes place through the wT state (169,173), 5 bands, Callear and Pilling (175) suggest that the C2T1 (v = 0) interacts with the aT as shown in Fig. V-11 and that the dissociation energy is 6.496 eV. V-5.3. Photodissoc Incident Wavelengths above 1910 A. The observed photodissociation products must originate from reactions of an electronically excited state since photon energies are not sufficient to break the bond, ‘The reaction products at 2144 and 2265 A irradiation are Nj, NO,, NzO. The quantum Yields are ®y, = 0.19, Dyio = 0.096, Dyo = 1.05 (9, 453, 681). VAS. Nitric Oxide 175 Imeor~oc%) wen om) Rad 2 Potential Curves of No V-I1, Potential energy curves for NO. From Herzberg et al. (462). The off is drawn according to Callear and Piling (175). AC the 1990, 1930, and 1860 A tines, the products are Nz, 2, NOx N,O (656). The quantum yield of NO disappearance is 1.45. A probable mechanism proposed to explain the photochemistry is No. No* (v-17) NO* + NO+2NO (v-18) O* + NO=N, + 07 (v-19) NO* +NO+N,0 +0 (20) 2NO + 0;+2NO; (v2) 0 +NO+M-+NO; +M (v.22) Incident Wavelengths below 1910 A. Hikida et al, (471, 4712) have ob: served a weak fluorescence of the fl’ = 9) bands when NO is illuminated by the 1849 A line, Since the incident photon energy is above the dissociation limit ofthe f system, the major path must be dissociation. The photolysis products at 1832 A (366) are N, and O;. Since the mole cule is probably raised to the C71 (v' = 1) level at this line, it would dissociate176 Photochemistry of Diatomic Molecules immediately (<1 nsec) into N +0. A likely mechanism at 1832 A is NOSN+0 (v-23) N+NO+N, +0 (v.24) O+NO+M-+NO; +M (v.25) 0+04+M+0,+M (v-26) “The quantum yiekd of N3 is expected to be unity, although the yield has not been measured. The photolysis of NO. by a hydrogen discharge lamp 1 aod A} yields mainly Np and NO, [Leiga and Taylor (624)] with quantum Yilds Dy, 202-04, Dyp, = 0.3 0.1.0 yyy OK LX ALTATO A (624, 865) the products are Na,/NO,, NO" with quantum yields by, = 0.3 0, Gay, = 6 Ll, @yjg = 002 0.1, and Oyo = 13 27. Quantum yields are dependent on the pressure and the flow rate. Produet NO is not found ina flow system In a static system N,O is probably formed by (624) N+NO;-+N,0 +0 (v2) The result that ®y, <1 in vacuum ultraviolet photolysis indicates that some electronically excited states produced may not cisociste immediately ‘This is supported by the results that emission bants from several excites NO states have been observed with 1470 A excitation [Young et al. (1070)} On the other hand, Stuh! and Niki (950) have found that O atoms are produced with light of wavelengths above 1600 A in the pressure region where the reaction of an electronically excited NO can be neglected. It is likely that both the production of excited NO and dissociation take place in the vacuum ultraviolet. ‘The ionization of NO occurs below 1338 A (9.266 eV) (1020). The photolysis at the Kr lines (1165, 1236 A) (624) leads to the formation of ions NOSNO* +e (v.28) ‘The NO* ions must eventually be neutralized to produce some stable excited states since ®y, < | is obtained, An increase of y, with an increase ‘of NO pressure indicates the occurrence of the pressure induced dissociation NO* +NO+N+0+NO (v-29) \V-S4, NO in the Upper Atmosphere (214) Nitric oxide is a minor constituent in the upper atmosphere (10 molec em * stan altitude of 105 km) (691). tis probably formed from the reaction, O('D) + N,0 + 2NO v3) ¥-6, Oxygen 177 The ionization of NO by the Lyman-a line i the main source of ions in the D region. The photodissociation of NO in the upper atmosphere occurs from the A7E* (v’ > 4), BF (e > 7), and CI (v' 2 0). The dissociation rate of NO by the solar radiation is proportional to the integrated absorption coefficient of various bands (that i, the oscillator strength). From Table V4 it can be seen that absorption by the (12.0) and 5 bands is most important in leading to photodissociation In the mesophere and stratosphere the effect of the absorption by the Schumann-Runge bands of O, on NO dissociation must be considered Because of the large absorption by Op in the region of the fi (12,0) band (1760 to 1776 A), photodissociation of NO above about 30 km is brought about mainly by the absorption of the 3 (1,0), (0,0) bands at 1830 and 1900 A, respectively [Cieshik and Nicolet (214)] V-6. OXYGEN V-6.1. O,07E,-) The ground state of oxygen is X*, DAO ~-O) = 5.115 + 0.002 eV (24) Very weak absorption bands in the region 2500 to 3000 A correspond to the forbidden transition A°E,'-X°E, (see selection rules 1-102). The band system is called the Herzberg I band, Second absorption bands in the region 1750 to 2000 A correspond to the BE, X'S, transition and are called the Schumann-Runge system, The region 1300) 6 1750 A is continuous and is called the Schumann-Runge continuum. Below 1300 A numerous Rydberg transitions have been observed [Yoshino and Tanaka (1066)} The absorption coetficients in the region 1100 to 2000 A are given in Fig. V-12 and the absorption cross sections of the O, continuum in the 1814 to 2350 A region are given in Fig. V-13. The potential energy curves are given in Fig. V- 14, Besides the two band systems already described, the two extremely weak systems bE XZ, (5380 to 7620 A) and a,-X°E, (9240 10 15,800 A) have been observed in atmospheric absorption. The former is called the atmospheric bands and the latter the infrared atmospheric bands The convergence limit ofthe Herzberg I bands isat 2424 A, corresponding to the production of OPP) + OCP), Below 2424 A ties a weak continuum (1920 to 2430 Ay [Hasson and Nicholls (447Y} The Schumann-Runge bands converge 10 the limit at 1750 A corresponding to the production of O(*P) + O('D). The integrated absorption coctlicients of the Schumann-Runge system from (0,0) to (20,0) have beenk 0. bo" 1z00 "1900 A 200: 10 100 a ke os e 0 Woo soo 120 vdeo A A Fig. V-12. Absorption coefficients of ©, in the region 1100 to 2000 A. & is in units of atm” cm=?, °C, base e. 1300 to 1700 X, Schumann-Runge continuum. 1750 t0 1950 A, ‘Schumann-Runge bands. From Watanabe et al. (1014), reprinted by permission. Copy: right 1953 by the American Institute of Physics. Fig. V-13. The absorption cross sections ofthe (0; continuum inthe 1814 to 2380 A region. 0 units of 10°22 cm? molee™*, base e, at om temperature. The absorption cross sections fre measured. at minima between the well Separated rotational lines of the ‘Schumann- Runge bands for 1-< 2025 A. o increases with pressure probably a8 a result ofthe formation Of Og. The data are values at the low pressure Timi: From Ogawa (758), reprinted by permi- son, Copyright 1971 by the American Tate of Physics. 178 V6. Oxygen 179 V-14, Potential energy curves of Oy. S-R, Schumann-Runge bands; H, Herzberg, bands; A-A, atmospheric bands. The line-brondening was observed at «” = 4 of the B°E, state at which point the repulsive IT, state crosses the BYE; state, See Murrell and ‘Taylor (726). From “Dissociation Energies and the Spectra of Diatomic Molecules by Gaydon, 3rd Ed. 1968, . 74, reprinted by permission of Associated Book Publishers Lid determined (104, 341, 444), They are given in Table V~8. Ackerman et al. (38) have measured the absorption coefficients for individual rotational lines in the region 1750 to 2050 A. The oscillator strengths of the Herzberg I bands from (4,0) to (11,0) have been measured by Hasson and Nicholls (446). An absorption coefficient of 0.30 + 0.03 atm~' cm™ at the 1216 A line has been determined by several workers (381, 753). Photochemistry. The threshold wavelengths for the production of O(*P). 0('D), and O('S) are given below. ‘Threshold Wavelength (A) 0,8 oem +0ep) 22 0; Hour) + OV'D) 1730 0, S opr) +0r's) 1332 ‘Ackerman and Biaume (37) have observed that rotational lines become dif fase ato’ = 4, 8, and LI for the Schumann-Runge system. They attribute the difluseness to predissociation. A line width of 3 em~! observed by them implies a lifetime on the order of 10°" sec for the (4,0) level. It is suggested by Carroll (192) and Murrell and Taylor (726) that predissociation is due to the crossing of the repulsive180 Photochemistry of Diatomie Molecules Table V-8. Oscillator Strengths of ‘Sehumann-Runge Bands of O;" Oscillator Oscitatoe Band Strength Band Strenth (0.0% 33 (—10F (0P—353(-9) 1,0) 2.74(-5) 0) 269(=8) (12.0) 3.5845) GO 154(-7) 13,0) 366(~5) (40) TANL=7) (14,0) 3694-5) (5.0) 2KO(—6) (15,0) L745) (6.0) 440(=6) (16,0) 3.3145) (0) RIS(—6) (ITO) 161-5) 80) 122(-5) 180) 203-5) (8.0) 150(—3) 19.0) 74(—5) (10.0) -205(~5) 20,0) L351—5) From Farmer etal 341) rom Hasson etal (444), 10) means x 10" * “at = 4 of the B°Z2. This is shown in Fig. V-14. The suggestion is supported by the observation that the Schumann-R unge emission bands are present only up to r° = 3, Furthermore, from the effect of added gases on the formation of O produced from the photolysis of O, at 1849 A, Volman (994) concludes that the O,(B°, ) predissociates at v’ 2 8. Washida et al. (1011) hrave found that the quantum yield of © production from the photolysis of 0; at 1931 A is only 0.3 at O; pressures from 300 to 1300 torr. The low quantum yield of O, was explained by collisional deactivation of the O.4B'Z, i! = 4) formed by absorption of the 1931 A line. However, this conclusion seems contradicted by the finding that the r’ = 4 level of the BPE, has a lifetime of only 10"? sec. The predissociation probabilities for various vibrational levels of the BIZ, state have been calculated (726) assuming a repulsive curve that crosses the BE, state near = 4. Both at 1849 (1011) and at 1470 A (954) the quantum yield of O formation is 2, indicating a direct dissociation 0, 40+0 way O+0,+M+0,4+M (V-32) Below 1750 A the production of O('D) is energetically possible. The produc: tion of OC'D) in the steady state photolysis of Oy at 1470 A was directly demonstrated for the first time by Noxon (745) by detecting a very weak emission at 6300 A due to the transition O('D) + Ot"P). The quantum yield for the production of O('D) in the primary process at 1470 A is uncertain, V6. Oxygen 181 Noxon calculated the rate constant of O(*D) quenching by O, on the basis of unit quantum yield and of the equilibrium concentration of O('D) atoms. His value of 6 x 107 '! cm? molec™! sec™' agrees well with 7 x 10°" cm? molec”! sec™' obtained independently (456), indicating that the assumption of unit quantum yield may be justified, Below 1332.A the production of O('S) is energetically possible. Filseth and Welge (348) have observed an emission at 5577 A due to the transition O(*S) + O('D) in the Nash photolysis of O; below 1340 A. The intensity isso weak that Xe has to be added to induce the transition. No quantum yield of O('S) production has been measured. Recently Stoncet al (937) have measured the flight time of O atoms produced in the fash photolysis of the molecular beam of O> in the vacuum ultraviolet, The O atoms are detected by the chemiionization reaction with samarium. The technique is similar to the one described in Section Il -4.1 The released kinetic energies of O atoms by 1470 A photolysis have a distribution with a maximum at 1,35 eV, indicating the process 0, 4 00°) + OD) (The photon energy corresponds to the sum of the bond energy, the elee- tronic energy of O('D), and kinetic energy of O atoms.) The production of O('S) at 1200 and 1240 A appears to be a minor process. Photodtissociatiqn of O, in the Upper Atmosphere. ‘The source of O atoms above an altitude of 50 km is mainly from the photolysis of O, in the Herzberg | and Schumann-Runge continua (488), The predissociation of O in the Schumann Runge bands (e’ > 3) [Wray and Fried (1054)] is the additional source of O atoms between 65 and 95 km. Supporting evidence of the Predissociation is that no fluorescence of the Schumann-Runge bands above # > | has been observed in the upper atmosphere A small amount of O('D) is produced from the ¢” = 1 and 2 levels by absorption of the solar radiation below 1850 A ofthe Schumann-Runge continuum (40) contributing to O('D) atoms in the mesosphere and stratosphere V-62. O,a'A,) 7 : The electronic energy of O,(u'A,) is 0.977 eV. The ionization potential is 11.086 eV. The O,(u'A,) is metastable with a mean life of 64.6 min [the transition probability A= 2.58 x 10"* sec! (54). since the transition «'d,-X3E, is strongly forbidden by electric dipole. The (0,0) band at 12,686 A, known as the infrared atmospheric band, is & prominent emission band in the airglow. The absorption spectrum of ©,('A) has been measured in the vacuum ultraviolet (39, 227, 754). A diffuse bund at 1442 A is very strong (absorption coelticient 1548 atm! em™!) (754),Photochemical Production. The direct production of O,('A) from the round state by light absorption is not possible since the transition i highly forbidden. However, O,('A) is a primary product of the photolysis of O; in the Hartley band (see Section VI-11) " 0s 01) + 0x) (V-33) ‘The ©,('4) state can be detected by measuring the ionization current (682) produced by light absorption below 1118 A Owu'd.v" = 0803 +e rea) or by absorption at 1442 A. The decay of the 1442 A line has been measured following the Nash photolysis of Oy (227) from which quenching rates of O,('A) by He, Ar, Kr, Xe, Nz. Hp, CO, and O, have been reported Emission at 12,700 A also indicates the production of O,('A). The intensity can be measured by a germanium photodiode cooled by liquid nitrogen in conjunction with a proper interference filter (351, 923, 1028). Reactivties of 04°). The 0) is stable against collisions with most gases (227), The largest quenching rate constant has been obtained for the reaction with Oy with ky, = 4 x 10°! cm? molec! see! (227) 0,°A)+0420;+0 hss v.35) (sec Table V-9), Table V-9. Comparison ofthe Rate Constant A, for Quenching O,(aA) and O4(6"E") by v. 565 at 300K A, for O02") (eri? molec" see!) 0 10's wo we + From Coltins and Husain 227) unless otherwise note, * From Filseth eal (350) unless otherwise noted, “From Steer etal (923), * From Gipin et a9). V6. Oxygen 1X3 O,{a'A) in the Upper Atmosphere, Emission from the O,("A) has been observed in the upper atmosphere (30 to 80 km) (744). The maximum concentration, located at an altitude of about 50 km, is estimated to be 4 x 10! molec cm”. The most likely process for the production in the upper atmosphere is the photolysis of O, in the Hartley continuum (2000 to 3000 A), V-6.3. O,0'E,") The electronic energy of O,("E) is 1.626 eV. The ionization potential is 10.437 eV. The mean lifetime of O3("E) is 6.9 sec (A = 0.145 sec” ') (1007) ‘A more recent value is 12sec (4 = 0.082 sec™!) (1000), The prominent cmission bands at 7619 and 8645 A in the day glow are the (0,0) and (0,1) bands of the transition "Ey +95, . The (0,0) band is called the A band (the atmospheric band). The vacuum tltraviolet absorption by O,('E*) has been detected recently by Alberti et al. (39). Photochemical Production. The production of O,(61E*) from the ground state O; by light absorption is negligibly smail, The O,(°E") is produced elficiently from (1068) O('D) + O; + OE") + OCP) (v-36) with a rate constant of 6 x 10-'! em? molec”! see” (745). The O(1D) atoms can be generated from the photolysis of 0, or O,. Quenching Rates. Quenching rates of O,(b'E") by various gases have been measured by following the decay of the 7619 A band (Filseth et al. (350) and others (80, 282, 398, 515, 745, 752, 99)]. They are shown in Table V-9. ‘The O,('E") is also produced from the energy pooling reaction (45, 282, sis) 0,('A) + O,('A) + 0,CE) + OXC'2) (w.a7) The quenching rates for O,(b*E*) are in general much faster than those for 0,u'A) as shown in Table V9 O,{b'E*) in the Upper Atmosphere. The atmospheric band of O, observed in the upper atmosphere (40 to 130 km) indicates that the O,('E") is produced by photochemical processes (1000). The most likely process is the photolysis of O, in the Schumann-Runge continuum followed by the energy transfer reaction (350) 0; + hy + OU'D) + OCP) (38) OUD) + 0, + OPP) + OSCE") (39)184 Photochemistry of Diatomie Molecules V-7. SULFUR (S,) The ground state of S; is X°E,. The bond energy is Dy(S—-S) = 4.37 + 0.01 eV. Absorption starts at about 3600 A at 100 C. The absorption spectrum in the region 2420 to 3600 A corresponds to the transition B°E, XPE,. Second (1650 to 1797 A) and third (1650 to 1708 A) absorption spectra correspond to the CE; -X*E, and D'M,-X°E, transitions, respectively [Rosen (24)} Ricks and Burrow (830) have obtained the predissociation limit from a rotational analysis of the emission and absorption bands of the BYE, XS, system of S) vapor. The limit is at 35,999 + 2.5 cm” ', corresponding to the products SUP,) + SCP,). The predissociating state (similar to Rin Fig, IT 5)is identified as the 1, state. Meyer and Crosley (700) have measured the Franc the system B°E, XZ, using resonance excitation to They have also obtained lifetimes of 20.7 + 1.4 nsec(o! = 3, N’ = 42,J° = 43) and 18.3 + L4nsec (v' = 4,N’ = 40.J° = 41) for the same system (699). Smith (911) has obtained 16.9 + 3.5 nsec by the phase shift method. The SE, is a product in the photolysis of $C; [Donovan etal. (307)] -Condon factors for 3 and 4 levels. V-8, HALOGENS V-8.1. Fluorine The ground state is "Ej; DF —F) = 1.56 + 0.02 eV (28). The absorption coefficients in the region 2000 to 4000 A are given in Fig. V-15 as a function of wavelength. Only a continuum has been seen corresponding to a transition to the repulsive state A'T,. A series of Rydberg states is observed in the vacuum ultraviolet (24) V-8.2. Chlorine The ground state is 1, ; De(Cl—Ci) = 2.479 eV (626), The very weak banded region 4780 to 6000 A represents a transition to the B°TI(0;) at Fig. V-IS, Absorption coefficients o 2000 to 4000 A. € isin units of Imol™ cm”, base 1 at room temperature. Reprinted with permission from sree tooo T4000 RK, Steunenberg. and RC. Vogel, Copyright by the A American Chemical Society. inthe region V-& Halogens 185 40 29) j zoo ape. sg00 4800 16, Absorption cocficents of Cl, in the region 2500 to 4500 A. € is in units of {Imot™' em=*, base 10 at room temperature. From Gibson and Bayliss (393), reprinted by permission: Copyright 1933 by the American Institute of Physics. 2.188 eV. The banded region is followed by a weak continuum in the region 2500 to 4500 A. The absorption coefficients in the region 2500 to 4500 A are given as a function of wavelength in Fig. V-16. The laser photolysis of chlorine molecules at 3471 A by Busch etal. (159) indicates that the Cl atoms are both produced in the ground state, *Py,., from a repulsive 'T(1,) state ‘The photolysis in the visible banded region isexpected to yield ?Pyya + *P ya, corresponding to the B10, ) state. ‘A second continuum lies in the region 1800 to 1950 A followed by various Rydberg transitions in the region 1070 to 1870 A [Lee and Walsh (621)]. V-8.3. Bromine The ground state is "Ej ; Do(Br~ Br) = 1.971 eV (626). The weak banded aabsoption region 6450 10 8180 A corresponds to a transition to the A°IM(1,) ‘The second banded region 5110 to 6400 A represents a transition to the #°T105), A band progression in this region leads to the convergence limit at 5108 A followed by a continuum in the region 3000 to STI0 A. In the region 1560 to 300A another continuum is observed. The absorption coefficients in the region 2000 to 6000 A are given in Fig. V-17. Potential curves are given in Fig. V-18. The A°I1(I,) state dissociates into ground state Br atoms, *P,,2, + ?Py,2, while the B°IK0; )state yields one metastable *Pijz and one ground state ?Py,p atom. Kistitkowsky and Sternberg (571)190 Faviocnenmstry op Biatonue totecutes te Fig. V-IT, Absorption concent of Beye fa ants ofl mol ems ba 10 ak se 2 ee 10. oom temperature. The arow dws the convergence limit in the Ns )-"E . trasition leading. te. the production See IST BPP) + BrP.) From Calvert and seb0 Pitts (4), p. 184, reprinted by permission A of John Wiley & Sons. have shown that the quantum yield of Br atom production is nearly inde pendent of wavelengths between 4800 and 6800 A. Above 6300A the incident photon energy is not sufficient to break the bond of bromine molecules in the lowest vibrational and rotational levels of the ground state. Photodissociation above 6300 A can be understood if the light absorbing molecules are originally in high vibrational and rotational levels of the ground state. The sum of the photon and internal energies is equal to or exceeds the bond energy in analogy with NO, photolysis described in Section 1-4.3. At 7150A no bromine atoms are produced. With 6940 A laser light, Tiffany (971) has found that bound excited molecules are formed in the ST1(1,) state, 1% of which undergo dissociation by subsequent collisions. Oldman et al. (779) have recently studied the photolysis of Br, by a polarized pulsed laser in the visible and ultraviolet regions. ‘At 5324 A bromine molecules dissociate mainly from the A*I1(1,) into ground state Br atoms. Apparently the B°11(0; ) state is not formed at this wavelength. At 4662 A the main dissociation is from B°11(0,") into Br(?P,,3) and Br(?P,;). To a smaller extent dissociation from A°1(1,) and 'T1(1,) into Fig. V-18, Potential energy curves of Br;. After Kistiakowsky and Stera- . stitute of Physic. Absorption of light Pt yy (261) a S435, 5940, 6140, and 6800 A leads thy 'Pg (281) to the contincum of the T1(L,) state hich discocate toms, *Pya Abe produces the 11(02) Associate Into two a) interaction with the repulsive, state ‘or proce one normal and one excited ftom, ¥-8. Halogens 187 ground state atoms has been found. (The threshold energy for the production Br(@P,,,) + Br(2P;,,) is 243 eV corresponding to 5106 A.) Photolysis at 3471 A yields two ground state atoms from the state 'TI(1,). Capelle et al. (186) have measured fluorescence lifetimes and quenching cross sections of vibrational levels from o' = I to 31 of the B°I10,’) state of Br, molecules. The lifetimes vary from 1.3 (v' = 27) to 0.14 psec (v' = 17) Lifetimes must be much shorter than the radiative life since in this absorption region (5130 to 6260 A) photodissociation is predominant (571). ‘The lifetimes and quenching cross sections of rotational levels in the B°TKO3) state have been measured near the dissociation limit by McAfee and Hozack (671). The observed lifetime is on the order of 3 ysec. Bemand and Clyne (94) have found excited Br atoms (55, “P42. *Psy2) in the vacuum ultraviolet photolysis of Br: V-8.4, Iodine ‘The ground state is "Ey ; Da(I—-I) = 1.542 eV (626), The banded absorption region 8300 to 9300 A corresponds to a transition to the A*TI(1,) at 1.463 eV and the banded region 4990 to 8400 A corresponds to a transition to the PIO; ) at 1.949 eV. The convergence limit of the vibrational progression ‘of the B°I1(0;) state is at 4995 A. The banded region is followed by a continuum in the 4000 to 4990 A region. The 1800 t0 2000 A region is also a continuum (Cordes bands). The region 1600 to 1800 A shows various discrete bands. Figures V-19a and V-19b give the absorption coefficients in the region 1000 to 6000 A. Figure V-20 shows vibrational structure of the absorption bands in the region 5000 t9 6500 A. The convergence limit at 4995 A is shown by the vertical arrow. The AM(1,) state dissociates into two normal I atoms (*Pyj2+7Ps)2) while the B°TK0;) state yields one normal and one excited atom (2P,,; + 2P,)2). This is shown in Fig. V-21 ‘The underlying continuum between $000 and 6500 A may be associated with a transition to the repulsive 'TI(L,) state, which dissociates into two ground state I atoms, A transition to the B°TT below the dissociation limit yields electronically excited 1,, which either predissociates into ground state atoms by way of the repulsive "TI state oF returns to the ground state by fluorescence, Brewer and Tellinghuisen (147) have measured the relative concentrations of I atoms by the resonance fluorescence technique in the steady state photolysis in this region. The quantum yield of [ atom produc tion varies with the wavelength of incident light, as shown in Fig, V-22. where the quantum yield at 4920 A is taken as unity. The quantum yields are dependent on the vibrational levels’. When ois low the quantum yield is near unity but it decreases at higher v, reaching a minimum near v= 15. This is explained by predissociation by way of the 'TT, which crosses the188 Photochemistry of Diatomie Molecules 49954 1 Esso: : wees ac whet : ae a : a a A Fig. V-19. (a) Absorption coefficients of 1, 28 a function of wavelength in the region 4000 to 6000 A. Units, Tol" em"; 70 £0 80°C; base 10, The arrow shows the Con Nergence limit in the BPIT(0;}-X'E transition leading to the production of 1@2P,,.) + 1GP,,)- From Calvert and Bits (3), p. 184. Region 1800 to 2000 A (Cordes bands): units, (10 Samson (728), 10°" (em?) corresponds to 27 (atm cn” Of Wiley and the American Institute of Physis. Copyright 1970 by the American In- stitute of Physics. (6) Absorption cross sections of I, in the region 1000 to 2200 A. Units, 10°" em; base e, room temperature. From Myer and Samson (728), reprinted by permission. Copyright 1970 by the American Insitute of Physics. B'N near the bottom of the potential curve as indicated in Fig, V-21. The TI state must cross the BM state again near v = 25 (2 = 5500 A) where the dissociation quantum yield shows a subsidiary maximum. The measured me of fluorescence changes accordingly. The Muorescence lifetime is shortest at 1° = 4 (0.53 jsec) and increases smoothly up to 1 = 13, then decreases (852). This dependence of lifetime on the vibrational level may be Ee? L aM sob a a Fig. V-20. Absorption spectrum of 1; showing theo” progression (o” = 0) leading to the ‘convergence limit at 4995 A (indicated by the arrow). The transition ia this region is BN(0;)-X"E;.. Above 6000 A contributions from +” = 1 and 2 become significant, From Capelle printed by permission. Copyright 1973 by the American tty B°n, ot MH, | a Pat Pay, a 3.0, 2 Rf 4 ig. V-21. Potential energy curvesof Ly The A"II(L,)statedissociatesimto®Py. "Py atoms while the H°11(0;) yields ?P, 2 + *P4.z atoms, The ‘II(,) repulsive state crosses the 8°11 state near the lowest vibrational level, From Brewer and Tellinghuisen (147), reprinted by permission. Copyright 1972 by the American Tnstitute of Physic. 189190 Photochemistry of Diatomie Molecules ay. Fig. V-22. Quantum yield for photodis ofl; (dhe production of I atoms) as a function of wavelength, ‘The quantum yield approaches unity at both ends. The results are explained on the basis of direct dissociation from the 'TI(1,) repulsive state and of predissociation from the B°11(0;) state, which iso” dependent (a mini- 15,2 submaximum near o” = 25). From ‘Tellinghuisen (147), reprinted by per- copyright 1972 by the American Insitute of mission. Physics. explained by the simultaneous occurrence of fluorescence ciation as follows. “The measured lifetime + can be expressed by the pure radiative lifetime and the rate of predissociation k, \d_predisso- c=— +k, (v-40) tte ‘Since the radiative lifetime is nearly independent of v’ (852) it can be seen that the measured decay rate 1/r is proportional to ky, which in turn is proportional to the quantum yield of 1 atom production. Therefore, the wavelength dependence of decay rate follows approximately the quantum yield curve shown in Fig. V-22, that is, the decay rate is faster when the ‘quantum yield of atom production is larger. However, the exact correspon- dence may not be expected, since both the B°I1 and 'T1 states contribute to the I atom production, while only the B°M1 state gives rise to fluorescence. ‘Then the percent absorption due to a transition to the BIT state must be known at each wavelength. Lifetimes and quenching cross sections of rotational levels in the B°T1 (0) state have been measured by Broyer et al. (153) and by Ornstein and Derr (781), The production of iodine atoms ?P,j., *Pyy2 was observed by absorption in the vacuum ultraviolet following the flash photolysis of 12 above 2000 A(296). While ?P j Latoms are produced its not certain whether the ratio of the metastable to the ground state population is 1:1 Using pulsed, polarized, monochromatic light of wavelength 4649 A, ‘Oldman et al. (778) have shown that not only the B°IT continuum corresponding to the production 2P,,. + *P,,., but also the 'IT state yielding 2Py). + #Pyja is formed by light absorption at this wavelength. Accordingly, the production of metastable 7P,,2 atoms is much less than that of ground state atoms. Photolysis at 2662 A by a polarized pulsed laser yields 1(?Psya) + 1@Py/2) [Clear and Wilson (218)}. The dissociation is probably from the C°E"(1,) as assigned by Mulliken ¥-9, Interhalogens 191 V-9, INTERHALOGENS. V-9.1. Bro Monochloride The ground stae is X"E*; Do(Br—Cl) = 223 + 001 eV. The banded absorption region 5500 to 6771 A is ascribed to a transition to the B°M(0"). A continuum follows in the region 3520 to 3600 A. Discrete bands (302) are’ observed in the regions 1613 {0 1656, 1539 to 1573, 1483 to 1512, and 1383 to 1415 A. The primary process by absorption above 2000 A is (302) BrCl + hv + Br? P sia) + CIPPy2,4)2) (v-41) ‘The fluorescence lifetime and quenching cross section of the BHO") state of BrCl near the lowest vibrational level have recently been measured by Wright etal. (1055). The observed lifetime is 18.5 + 3 ysee and the quenching ross section by BrCl is 0.1 x 10~*° cm? V-9.2. Iodine Monochloride ‘The ground state is XE* ; Da(I--Cl) = 2.151 + 0.001 eV (24). Closely spaced red-degraded absorption bands appear in the region 5500 to 8800 A. These are attributed to transitions to the A*I1(1)(5730 to 8770 A), B*TK0* )(5500 to 5730 A), and B'(0*) (5600 to 5700 A). A continuum appears in the region 2200 10 2650 A. Various discrete transitions appear in the vacuum ultraviolet, namely, 1795 to 1910 and 1670 to 1740 A regions. Flash photolysis in the region above 2000 A leads to the production of I@Py,2) and probably CI?P,,2) (302). Absorption above 2000 A consists of a continuum and the discrete B(0°}-X 'E* transition. The production of ClC2P;)2) was not observed probably because of the rapid reaction with ICI. Fluorescence is observed with light of wavelengths 5820 to 6100 A, which lie below the dissociation limit at 5763 A. The lifetime is on the order of 100 jee (479) with some variation with excitation wavelengths. Y-9.3. Iodine Monobromide ‘The ground state is X"Z*, Do(I—Br) = 1.817 + 0.001 eV. Closely spaced absorption bands appear in the region $450 to $060 A. These are attributed to transitions to the A°I1(1) (5740 to 8060 A), B°TT(0*) (6200 to 6765 A), and B(O*) (5450 to 6190 A). A weak continuum lies in the region near 2700 A followed by discrete transitions in the regions 1867 to 1975 and 1728 to 1800 A. Numerous bands are observed in the 1300 to 1600 A region (314). Flash photolysis above 3000 A produces I(?Ps/2) and Br(?P,,2). which are detected by absorption in the vacuum ultraviolet (302). The B°MT state appears to be responsible for the production of the ground state f and the metastable Br atoms.192 Photochemisry of Diatomie Molecules The photolysis at 5310 A by a pulsed polarized laser produces mainly ground state atoms and to a smaller extent 12P,,2) + Br2P),) atoms [Busch et al. (160)). Both processes are associated with the 0" state V-10. ALKALI IODIDES. V-10.1, Sodium lodide The ground state is X'E*, Do(Na—I) = 2.97 eV (24). Three continuous regions of absorption (24) have been found in the ultraviolet with the absorption maxima at 3240, 2580, and 2120 A. The dissociation products corresponding to the three continua are, respectively, Na(2S) + I2P3,2), Nal?S) + 1P),3), and Nal?P) + 1P3,2), The threshold wavelength of incident photons to produce the electronically excited Na(2P) is 2480 A. The quenching cross sections by H3. HCI COs, and HO for the sodium D lines have been measured as a function of exciting wavelength above 500°C. The quenching cross sections by HCI and CO; decrease with an inerease of reative velocities between the excited Na atoms and quenching molecules [Hanson (441), Earl etal. (332, 333)] V-10.2. Potassium lodide the ground state is X'Z"; De(K--1) = 3.35 eV (24), Three continuous regions of absorption have been found with maxima at 3260, 2610, and 2340 A. The corresponding dissociation products are KOS) + 1(?P 3:2), K(2S) + I@Py:),and KZP) + 1 Paya) respectively. Ormerod et al. (780) have studied the photolysis of KI with pulsed po- lavized light of wavelength 3472 A. From the angular distribution of the product | atoms dissociated from a molecular beam of Kl, they have con- ‘luded that the recoil 1 atom direction is nearly perpendicular to the electric vector of the polarized light. The results suggest « transition from the ionic ground state to a neutral excited state. V-I1, ELECTRONIC TRANSITIONS AND LIFETIMES OF SOME DIATOMIC RADICAI Diatomic radicals are often produced in their ground and electronically excited states as primary photolytic products or as reaction intermediates. Radicals such as OH and CIO are now believed to play key roles in air pollution of the troposphere and stratosphere, which is discussed in Section ViNt2 Reaction rates of diatomic radicals have frequently been studied by following time dependent optical absorption immediately after the radicals YAH. Electronic Transitions and Lifetimes of Some Diatomie Radicals 193 are formed. Alternatively, radicals formed in the ground state can be brought to Muorescing excited states by suitable light sources whose wavelengths are coincident with major absorption bands of radic intensity is approximately linearly proportional to the ground state radical concentration, reaction rates can be measured by the time dependent Muorescence intensity (see Section III 5) The steady state OH concentration in the atmosphere has been measured by the fluorescence technique using a dye laser tuned near 2820 A [Wang and Davis (1006), Davis et al. (267)] oF a microwave excited OH resonance lamp [Anderson (42)]. Rate constants of diatomic radicals such as OH, SH, ClO, and SO With atmospheric constituents are tabulated in recent publicitions by Hampson and Garvin (10) and by Anderson (1). In the following section we Dresent the main transitions, lifetimes, and a few reaction rates of some diatomic radicals of photochemical interest. The results are summarired in Tables V-10A through V-14 Since the fluorescence V-IL1. Diatomic Radicals Containing Hydrogen CH (Methylidyne). The ground state is X°T1; Do(C—H) = 3.469 + 0.01 eV. Both absorption and emission have been observed in regions 3143, 3900, and 4315 A corresponding to transitions to the C25", BE, and A2A states, respectively [Wallace (30)]. Radiative lifetimes of the A7A, B?E~, and C5* states have been mea sured by Anderson et al. (43), Fink and Welge (353), Hesser and Lutz (470), and Hinze et al. 473), These are given in Table V-10A, Various transitions in the vacuum ultraviolet have been observed by Herzberg and Johns (467). The CH molecule dissociates by absorption of light below 3200 A. The CH absorption has been observed in the flash Photolysis of diazomethane in the near ultraviolet by Herzberg and Johns (467) CH(A*A) emission has been seen by the photolysis of diazomethane and diazirine in the vacuum ultraviolet [Laufer and Okabe (605, 607)] Reaction rates of CH(X?M) with various molecules have been measured by Bosnali and Perner (122a) and are given in Table V-10B, The reactions are generally fast with efficiencies ranging from 1 to 001 Burnes et al. (61a) have detected ground state CH radicals in Name at atmospheric pressure by measuring the CH(A?A-» XM) fluorescence intensities excited by a tunable dye laser at 4315 A, NH (Umidogen), The ground state is X98": Dy(N—H) = 354 4 0.1 eV. Three systems of NH. AMT XE", eM a'A, and ef B'S" have been Observed both in absorption and in emission at 3360, 3240, and 4502 A.NH Vable V-10A. ‘State ven ah BYE ox ser aa mae an en ast Electronic transitions and Lifetimes of CH and NUT g (6) Atworpti 0 287 AX (a3ts A) 3188 BX (3600 3900 A) 39 CN (3144-3160 Ay ° Ls6t 2633 bx (a710 A) 36 AX (3200-3400 A) 5374 ea (3240 A) cb (4502 A) 022 dave (2530-4700 A) 194 Litetime 500 4: SO see 400 4 60 nsee 100 nsee 2S mee 178 msee 0146 ysee 0140-045 psce 0.43 see 0441 -0.30 pce 0.48 psec 18 + 3 nsec 46 # S nsce ( =0,Q branch) ‘Table V-10B. Rate Constants of CH(X*M1) Reactions with Various Molecules (1222) = From Ref 637 rom Ref 139. ‘ Products (em! mee“ see“) CO + NH 7 10 x 10°42,73 x 19° fon 17 107 x 0° co+ ont 410-8 AR x 10-8 45x 10°44 98 x 10-8 GH. +H 33 x 104.26 x 10" ‘Reaction fo form CH, + H is endothermic by 3 keal mol” “From Ref. 617% Ref, 353,470, 43 43,353, 470, 473, a 394, 162 394, 666 1086 389 352,912 916 352 516 912 912 4865 Vo11, Electronic Transitions and Lifetimes of Some Diatomie Radicals 19S ‘Table V-10C. Comparison of Reaction Rates between NH(a' A) and NH(*E*) (ent? mole”! see" !) Ni Reactant ata ae S 421077 = 18 x 10 60 x 10° 24 x 10719 - Rox 10" 49 10° 19 10°" - 93x 10°" = 41x10 12x10 Bx 10-9 85x 10" Bet Vax oo Box to 47x 10" 67 10" From Ref. 674, * Brom Ref 108s respectively [Wallace (30)}. The NH (X25, a'A, and cI) states have been observed in the sacuum and near ultraviolet photolysis of ammonia and hydrazoie acid [see Sections VIF Land VIT 9 and Hansen et al. (440)]. The NH(b'E') has recently been detected in the vacuum ultraviolet photolysis. of ammonia by Masanet et al. (666) and its reaction rate with ammonia has been measured by Zetzsch and Stuhl (1084), Lifetimes of 4111, b'E*, and TT have been measured by various workers and are given in Table V-10A. The dependence of lifetime on rotational and vibrational levels of 4°TT and c!M1 states has been observed by Smith et al, 916) Quenching of 4°TT and c' by various gases has been studied by Kawa- saki etal, (559). Rates of reaction of NH(b'E*) with CH,, CzHa, and CyHy are two orders of magnitude slower than the corresponding rates of NHlu'A) as shown in Table V-10C. The trend that more energetic NH(h'E *) react less rapidly than NH(a'A) is strikingly similar to the behavior of O('S), which is less reactive than O('D)as shown in Table V3.196 Photochemistry of Diatomic Molecules OH(H roxy), SH (Sulfur Monohydride), PH (Phosphorus Monohydride). The ground state of OH is X7M; DolO—H) = 4.394 + O01 eV. The first transition A7E*-X7I1 has been extensively studied both in absorption and ‘The OH (X7T1) can be generated from the photolysis of water, hydrogen peroxide, and nitric and nitrous acid. Reactions of OH(XM) with various hydrocarbons are important in understanding photochemical smog formation (see Section VIII-2). The OH(A7E") has been seen in the vacuum ultraviolet photolysis of ‘water, hydrogen peroxide, and nitric acid, The OH(4E:* jemission produced from OH(X?M1) by light absorption has been extensively used to measure OHLX?M1) reaction rates [for example, Stuhl and Niki (951)] The lifetime and predissociation of OH(42E") have been extensively studied by German (390), Smith (913), Sutherland and Anderson (955); see Table V-I1A, Quenching of the OH A7E* state has been extensively studied by Welge ct al. 1034), Hogan and Davis (477), Becker et al. (84), and Kley and Welge (376), The ground state of SH is X71], DSH) = 360 + 0.2 eV. The near ultraviolet absorption at 3237, 3241, and 3279 A corresponds to the A?E* Table VIIA. Electronic Transitions and Lifetimes of O, 11, and PLL fy ey Lifetime Ret on To (00) = # x 10-* 913 aE 4017 AX 0.69 psec (N" = 0) 390,913 (3064-2472 A) "dependent 2x6 (0.82 psec ("= 2) sa Predissociation > 955 (N= Mfr OD) toa BE! 8477 BA (4216 A) E+ 11.087 Gonsee ons 2nvee ons sHoovn oo AE" 38D AX 035 sce 2 (2240 Ay (0.28 yesce for SP) 85 PH x8 0 AT 3656" AX 0.44 pce 382 (3400 A) * Rots a. (842) V-H, Electronic Transitions and Lifetimes of Some Diatomiec Rusicals 197 ‘Table V-11B. Electronic Transitions of Higlt® System (9) (eion of Absorption) XE AM, 3.087 AX (4017 A) AM, 3503 AX (3500 A) BE 420 Bx (2950 Ay cr 4a Cx (2807 Ay “From Rete. 2, X71 transition, The corresponding emission is seen only from 1° = 0, indicating predissociation of the SH{A7Z") state for v' > 0 [Pathak and Palmer (798a)]. The lifetime of SH(42E") is 055 psec [Becker and Haaks (82)]. Several transitions have been found in the vacuum ultraviolet region (24), Ground state PH is X°Z, Do(P—H) = 30 + 0.3 eV. Near ultraviotet absorption at 3420 A is ascribed to the 4°M-X2E~ transition (24). Three band systems, namely, ' —u'A,"M = a'A, and °Tl — XE, have recently been found at 1625, 1595, and 1435 A, respectively, by Balfour and Douglas (514). The lifetime of PH(A°M) is 0.44 psec [Fink and Welge (352)] HgH (Mercury Hydride). The ground state is X?EZ; DolHg—H) = 0.37 eV (8). Four main transitions have been found near 4017, 3500, 2950, and 2807 A corresponding to the A2T,,,-X7E, 42M y2-X?8, BE-XPY, and C?E-X?E transitions, respectively, both in emission and in absorption [absorption by Callear et al. (177, 179)}. These transitions are shown in Table V-11B, New HgH absorption bands have been found by Callear and Wood (179) in the vacuum ultraviolet. The HgH(X7E) has been seen as the main reaction product of Hg(?P,) +H, Hg@P,) + Hy > HgH(X?E) +H The lifetime has apparently not been measured. V-11.2. Diatomic Radicals Containing Carbon CN (Cyano}, The ground state is CN) = 785 + 005 eV. ‘Two main transitions, A711 X?E*, BE" X2E*, have becn found both in19 emmaunemisiry of wiatomie Molecules absorption and in emission in the regions 4300 to 15,100 and 3500 to 4800 A, respectively ‘The X2E°* state has been observed in the photolysis of various cyanogen compounds in the near and vacuum ultraviolet. The B?E* and A211 states have been seen in the photolysis of cyanogen compounds in the vacuum ultraviolet [Mele and Okabe (692)}. Lifetimes of the 4211 and BeE* states have been measured by Jeunehomme (532), Cook and Levy (236), Luk and Bersohn (650), Liszt and Hesser (641), and Jackson (518). These values are given in Table V-12. Quenching of the B*E state has been measured by Jackson (518) and Luk and Bersobn (650), Cz (Dietomic Carbon). The ground state isa singlet X*E, ; DolC—C) 6.113 + 0.05 eV. Seven triplet and six singlet states have been found for Cy. The strongest and most easily excited system is the Swan bands, df, a°T], in the 4300 to 6700 A region, The emission lifetime has been measured by Fink and Welge (353) and is 0.2 + 0.05 psec. Electronic transition mo- ‘ments of various bands of the C molecule have been measured by Cooper and Nicholls (239), Table V-12. Electronic Transitions and 8 of CN and C, ‘System atomic & (Region of Radical State (eV) Absorption) Lifetime Ref. CN ET oO an LIM AX 140 nsee te’ = 10) 236 Red (4374 151004) 70405 pseetw s 9" $32 Slightly &° dependent wr 319 ax ons r= 0) 236 Violet (9590-4216 A) 63 4 3nsee 518,650 K’ dependent at boa os Enission (4000-5000 A) CG x 0 aT, 0.080" an, 248 dea 02-4 005 psee 353 Swan (4383-5165 A) ‘olisionally induced intersystem crossing fom CN(A#TI ~ B2E.*) observed at low pressures of BICN appeatsto support a value of 7 yace, See Rel 47a, "rom Rel 24 VAIL. Electronic Iransitions and Lifetimes of Some Diatomic Radicals 199 The ground state Ca1X'E, )is a primary product of acetylene photolysis The dll, state is formed from the photolysis of bromoacetylene in the ‘vacuum ultraviolet. [is also formed in flame and discharges through carbon containing compounds. The Swan system is a major feature of emission spectrum from the heads of comets. vu Diatomic Radicals Containing a Halogen; FO, ClO, BrO, and 10 The ground state of XO (X "Cl, Br, I) is XM; DolF—O) = 2.40 + 0.2 eV (220, 628), DelCl-O) = 2.7504 + 0.0004 eV (250), Dy(Br—O) = 2.39 + 003 eV (327), Dg(l--O) = 1.8 + 02 eV (327). The A*11-X711 transition has been observed in absorption in regions 2600 to 3100 [Coxon and Ramsay (250)]} 2890 to 3550, and 4200 to 4600 A. respectively, for CIO, BrO, and 10. Various electronic transitions of CIO in the vacuum ultraviolet have been found recently by Basco and Morse (68). Fluorescence from C1O(4?T1) formed by light absorption of the ground state has not been detected probably because of strong predissociation of the excited state [Clyne et al. (223)} The CIOLXIT) has been detected by optical absorption following the Mash photolysis of C10 and ClO, or by the reaction of CI with Oy. The latter reaction is an important source of CIO in the stratosphere [sce Section ViN-22], The XO(AM1- X7M1) transition is given in Table V-13 for CIO, BrO, and 10. Y-11.4, Diatomic Radicals Containing Sulfur SO (Sulfur Monowide). The ground state is XE~; De(S ~O) = 5.34 + 0.02 eV (225, 768). The transitions BE~-X°E", A'T-XE" have been ob- Electronic Transitions of CIO, BrO, and 10 r System Ste (@V)— (Region oF Absorption). —_ Ret. co eno an 382 Ae 24,327 (2600-3100 A) Bo |OxN Oo aM 3462 An 24,327 (2890-3550 Ay 10 xno wn 67) AEX ™ 14200-4600 A)200. Photochemistry of Diatomic Molecules served in the 1900 to 2600 and 2400 to 2600 A regions, respectively. The lifetime of the B75 state has been determined by Smith (911) (see Table V- 14), The SO(X°E") is formed as a primary product of the photolysis of SO; below 290A. The SO(4°T1, B22) states have been found in the vacuum ultraviolet photolysis of OSCl; [Okabe (768)] CS (Curhon Monosulfide), The ground stateis X'E* ; D(C —8) = 739 + 8.03 eV, The main transition is A'T1-XE-* in the region 2400 to 2800 A. The lifetime of the A*T1 state has been measured by Smith (911) and Silvers and Chiu (882) (see Table V-14). ‘The CS(X'E*) has been seen in the flash photolysis of CS, in the near ultraviolet, The CS(A'TI) has been observed in the vacuum ultraviolet photolysis of CS; (769) and SCCl; (774), Fluorescence from the CS(a°Ml) e hts been observed in the photolysis of CS, in the 1250 to 1400 A region ‘of absorption. The lifetime and quenching rates of CS(uT1) by various gases have been determined by Black etal, (118). & tegion of we) Absorption) Ret so 34,226 Mero wa (0.79 br "1303 ba Emission (9500 10,900 Ay an, 4748 AX (2400-2600 Ay BE 5161 BX It 3nsec 9 (1900 2600 A) cs ™ \ 0 wm 343 aa x Hoa dmsce 11K Emission (3400-3800 A) AMT 4810 aX 255425mee 911 (2400 280A) 176 4 M4 nsce 882 chapter V1 Photochemistry of Triatomic Molecules The photochemical processes of triatomic molecules have been extensively studied in recent years, particularly those of water, carbon dioxide, nitrous oxide, nitrogen dioxide, ozone, and sulfur dioxide, as they are important minor constituents of the earth's atmosphere. (Probably more than 200 Papers on ozone photolysis alone have been published in the last decade.) Carbon dioxide is the major component of the Mars and Venus atmospheres. The primary photofragments produced and their subsequent reactions are well understood for the above-mentioned six triatomic molecules as the photodissociation involves only two bonds to be ruptured and two fragments formed in various electronic states. The photechemical processes of these six molecules are discussed! in detail in the following sections, They illustrate how the knowledge of primary products and their subsequent reactions have fed in interpreting the results obtained by the traditional end product analysis and quantum yield n VE |. WA’ (1,0) The ground state of H,0 is ¥1A, with an H--O -H angle of 1052.16) the bond energy, DoH OH) = 5.118 + 0.01 eV (118.02 + 0.2 keal mol!) (28) rey ‘The absorption spectrum of water in the vicuum ultraviolet has been studied by Johns (533) and by Bell (92), Sharp rotational structure has been observed only below 1240 A (53%), The 1240 A bands have been assigned to the 'B,—'A, transition and is the first membes of the Rydberg series. The absorption coclicients of water in the vacuum ultraviolet have been mensited by Watanabe et al (1016, LOLS) and are shown in Fig, V1. The absorption coeficients of D,O have been measured by Laufer and MeNesby ih the region 1300 to 1800 A (60h) VIAL. Photdissociation ‘The vacuum ultraviolet photolysis of waiter bas heen reviewed by Me Neck and Okabe (684) and 1 nb Dy204 Piwtoicoustry Wf irualonue Stutecules 500, 200. 100. 0. ] K 20. | to. 5 2 j 1 300 © 00 | 1700 A 00. 200. Fig, VIL, Absorption coefficients. of k 100 ‘water inthe vacuum ul i 40. ‘is given in units of atm" cm", base ¢, O°. From 20 016), reprinted by permission. Copy- 1000) asl right 1953 by the American Institute of k Physics. 1400 to 1900 K Region. A major primary process in this region is the production of H and OH(X?11) HOH + OH(X?M) < 2420A (VI-t) ‘The flash photolysis of water in this region has produced OH(X?I1), which according to Welge and Stuhl (1033), is rotationally excited only up to N" = 5 and no vibrational excitation is found. The rotational distribution of OH is practically equal to that at room temperature, suggesting that the excess energy, the difference between hv and De(H—OH), is distributed between translational energies of H and OH [also see Masanet et al. (241, 665)]. The excited state of water responsible for dissociation in this region is considered to be the unstable A('B,) state [Horsley and Fink (485), Miller et al. (704)] The electron configuration of ground state water is (14,9724, 734 2A? and that of the first excited state A("B,) is (a, F2a, Fg FBa, PU 4) Viet. Water (HO) 203 The A('B,) state is derived from the promotion of a nonbonding electron in the 1h orbital to the 4a; orbital. Since the bond angle and the geometry change very litle by this promotion, the OH(X?T1) acquires very little angular momentum as the H atom flies apart from the molecule as has been described in Section II- 42, The second primary process that is energetically feasible and spin-allowed is H,OSH,+O('D) <1770A «vie2 ‘The production of molecular hydrogen to an extent of 6% of the primary Process at 1470 A has been suggested by Stief (929) from the photolysis of mixtures of water and ethylene. A simiar conclusion is reached by Ung (984) [AL 1470 A process (VI-2) is less than 0.3% of (VI-1) [Chou et al. (210)]. A more recent estimate for the ratio of (VI-1) to (VI-2) is 0.99:0.01 for 2 > 1450 A and 0:89:0.11 for the 1050 to 1450 A region [Stiet et al (935)). Stubl and Welge (948) have obtained, from flash photolysis of mixtures of H;O and 8 large excess of H, higher concentrations of OH than those from pure H,0. They attribute the production of excess OH to process (VI-2) followed by O('D) +H, + OH +H (vi) 1200 10 1400 A Region. The processes (VI-1) and (VI-2) represent main primary processes in this region, although (VI-2) appears to gain more importance in the second continuum [Stief et al. (935)]. Below 1350 A the following process occurs to an extent of up to 5% H,OMH+OH(E*) <1357A (Vi-4) The energy above the minimum ‘required for (VI-4) is transformed predominantly into rotational excitation of OH(4?Z*) [Carrington (191)] The observed rotational excitation of OH may be qualitatively explained from the electron configuration of an excited state of water responsible for dissociation. The excited state of water from which OH(4E:*) dissociates is considered to be the B('A\) state with the configuration [Horsley and Fink (485), Miller et al. (704)) (1a, )?24)(1,)°(344)(15 73845) That is, a bonding electron in the 3a orbital is excited to the 3s, orbital The promotion would result in an increase of an H-O—H angle. The transition to the B(',) from the ground state would therefore produce a highly excited bending vibration. A combination of antisymmetric stretching and bending vibration would yield the necessary torque to strongly rotate the OH(4?5) as the IT atom Mies apart, See Seetion II-6.5 p. 96.204 Photochemistry of Triatomic Molecules Fig. VI-2. (@) Absorption coefficients of H,S in the region 1800 to 3000 A. & in units ‘of mm” em” *, base 10, room temperature. 10~* (mim~* em”), base 10 corresponds to 1.91 (atm_* em”), base e. From Goodeve and Stein (410), reprinted by permission of he Chemical Society. (b) Absorption cross sections of 1,5 in the region 1200 ta 200) A. 2s given in units of 10° cm’, base e, room temperature. From Watanabe and Jars (1018), reprinted by permission. Copyright 1964 by the American Institute of Physics. VI-2. HYDROGEN SULFIDE (H,S) The ground state is X'A, with an H—S—H angle of 922° (16). The bond energy Do(H—-SH) is 391 + 0.2 eV (28). Absorption starts at about 2500 A with 4 maximum at about 1870 A. The absorption spectrum in this region is nearly continuous. The absorption coefficients in the near ultraviolet have been measured by Goodeve and Stein (410) and in the vacuum ultraviolet by Watanabe and Jursa (1018), They are shown in Figs. VI 2a and VE 2b. Gallo and Innes (382) have recently confirmed the 1391 A band as being due to the "By-"A, transition previously assigned by Price. VI-2.1. Photodissociation The primary process by light absorption in the near ultraviolet appears predominantly to be the production of H atoms and SH radicals HSNH4SH 2 10) and neighboring BE" (0° & 0) levels. Because of the long radiative life of 471. state (~7 psec) (532), itis susceptible to collisions even at x pressure of 10 mtorr, VI-S. CARBON DIOXIDE (CO,) ‘The ground state of CO, is XZ, (linear); the bond energy D(OC—O) = 5.453 + 0,002 eV (28). Absorption begins at about 1700 A. The absorption coefficients in the region 1050 to 1750 A have been measured by Inn et al (511), and more recently by Nakata et al. (730). The absorption coellicients in the region 1050 to 1750 A are given in Fig. VI 4a and in the 17200 2160 A region in Fig. VI-4b. The three peaks observed at 1474, 1332, and 1119 A are assigned by Winter et al. (1052) 0 the *A,, 'F1,,and *E," states, respectively, on a theoreti cal basis. Recently the measurement has been extended beyond 1700.A [Ogawa (755), Heimer! (461), Shemansky (871)] as the importance of the photochemistry of CO, in the lower atmosphere of Mars and Venus has been recognized. ‘The temperature dependence of the absorption coeflicients in the region 1700 to 2000 A has been measured by DeMore and Patupol (279). The results suggest that the CO, absorption coefficients in the range 1700 to VI-S. Carbon Dioxide (CO,) 208 1260 "doo" Woo A o is ee iterates ‘ients of CO, in the region 1050 to 1750 A. & is in units of 00" ca *, base, O°C: From lem eta (S11, reprinted by permissions Copyeght 1953 by the American Intitate of Physic () Atourption coefitents af CO, i te region 1720 to 2160 A. ks given in units of atm" cm", base, O°, From Opa (785), reprinted by permission. Copytigt 1971 bythe American nwtate of Pete 2000 A in the Mars atmosphere (200°) are approximately one half those at room temperature. Table VI-1 shows the threshold wavelengths below which indicated reactions are energetically possible vis |. Photochemical Reactions The products of the photolysis of CO, are CO, O;, and small amounts of , at all incident wavelengths, However, the quantum yield of CO is not always unity. Furthermore, the ratio ©,/CO is usually less than half that expected from material balance. It appears that wall conditions are an¥ tratomue Molecules Table VI-1. Photodissociation Thresholds of CO; in Angstrom Units for the Production of a 225° 1672 1286 1082 923 m2 920 803 702 * The threshold wavelength below which the disci tion of COs into COUXE") + OP) is energtially possible 5 important factor to determine the yicld of CO and O,. Table VI-2 summar- ‘izes the results of the CO, photolysis. The photochemistry of CO, may be conveniently discussed for three regions of absorption: («) above 1672 A where only the production of O(P) atoms is energetically allowed, () the 1200 to 1672 A region where the O{!D) atom production is predominant (©) below 1200 A where the production of both O('D) and O('S) is energet cally possible Above 1672 A, ‘The absorption by CO, in this region is extremely small (<0.4 cm"! atm~*) (755). The only energetically possible primary process is the production of OPP) co; ¥CO + OCP) (VEI6) ‘The primary photodissociation yield is unity at 1849 A (measured by the yield of OP) atom production), although the quantum yields of CO and ©; are much less than I and 0,5 respectively [DeMore and Mosesman (278)], The quantum yield of CO is 0.2 to 1, depending on wall conditions (278). The O3 to CO ratio is 00 0.4, which is less than the 0.5 expected from (VI-16) followed by the combination of O atoms 0+0+C0;+0,+C0, wri7, Tan and Heimer! (512) and K rezenski et al. (585), on the other hand, obtained ®co of near unity in the 1750 to 2100 A region and at 1849 A, respectively. ‘The CO yield at 2139 A is 0.16 (585), which may indicate the production ofa nondissociating excited state, although the results are much less conclusive than those at 1849 A because the absorption at 2139 A is only 1% of that at 1849 A. Ret 585 585 278 1062 9x2 983 346 846 301 1009 808 649 905 513 366 897 846 866 O,+M si Astinometry from NO Pressure independent (0.00220 tort) 2from Os = 14 from NO 3 z 2 : e s Ky x, = 14 from N,O photolysis, 3, from +0; +M Calibrated thermopile Calibrated thermopi qo = 0.75 at 14704 0, = 14 from N;O- Og, = 14 from N;0 %, = 2 from O> 0, = 2 from Oy Calibrated thermopile Photoionization yield of NO %, , 0,/co 0-04 03-04 = 004-011) 01-03 0-07 04-06 0-05 05-06 004-02 2-02 os + 005 035 + 00 005-02 00: 0 etror Quantum Yield ®o = 0.16 + 005 = 108 + 01 = 10" Bo = 03-09 =1040 = 05-06" Op = 02-085 co = 1.0 10" = 07-08" = 04-05 = 106 +01 Me value, eq = 027 ®%o 5 0 0 co = 10 (80 = 1) ep = 06 o, o Oo %o * Quantum yield of O atoms "Pro ‘Table VI-2. The Quantum Yields of CO in the Photoly the most 1750-2100 0 1633, 1200-1500 1048, 1066 1500-167 1236212 Photochemistry of Triatomic Molecules 1200 1 1672 K Region. The production of O("D) atoms is energetically possible inthis region CO, SCO + O('D) (Vi-8) The direct detection of O('D) by the emission at 6300 A in the steady state photolysis of CO, near 1470 A has failed [Young and Ung (1067), Clark and Noxon (216)], although O('D) atoms from O} photolysis near 1470 A have been detected, The failure to detect the emission must be due to the weak absorption of COs, rapid quenching of O{'D) by CO, and the long radiative life of O('D) atoms. However, the production of O('D) in the CO; photolysis is strongly indicated by the following observations: 1. O atoms produced from ©, photolysis at 2537 A are capable of exchanging with O atoms in CO, while O atoms produced from Oy by absorption of visible light do not exchange (558) 2. 0 atoms from N,O photolysis at 1849 Avexchange with those in CO; (1060). 3. When C'°0"%0-C!¥0!O mixtures are irradiated by 1470 A light, COMO is produced (73). These observations suggest that O atoms produced from CO, at 1470A must be in the same state as those produced from O, at 25374 and from N,O at 1849A , namely, O1"D). 4. The product, neopentanol, of the photolysis of CO, -neopentane mix- Cures: 16334 indicates that OD) atomsatre produced. Furthermore, the ratio neopentanol/CO = 065 obtained in a large excess of neopentane suggests that the quantum yield of O(*D) production is close {0 unity [Quick and Cvetanovic (821)}, since the same ratio of 0.65 is obtained for Nz photolysis at 2139 A. To explain the rapid exchange ‘of O('D) with CO3, Katakis and Taube (558) postulated the intermediate formation of COs. In fact, new infrared absorption bands found in the 2537 A photolysis of Oy in a CO, matrix at 50 to 60°K have been assigned to CO, absorption (713, 1028) Jacox and Milligan (520a) favor the thrce-membered ring structure with an O-—C—O angle of 65° from the analysis of infrared spectra of isotopic species of CO; in low temperature matrices. A new broad and weak absorp. tion band at 4060 A with an absorption coefficient of 1.1 +03 atm~! em”! isalso found in ©, —CO, matrix (551). However, no corresponding infrared absorption bands have been found in the gas phase photolysis [DeMore and Dede (277}) The photochemistry of CO in this region may be summarized as follows. co, 8C0 + 0D) 0('D) + CO, + COF COs + CO, + OFF) 200P) + CO, +0; + CO, VIS. Carbon Dioxide (CO;) 213 The lifetime of CO$ with respect to dissociation into CO + O(°P) is about 10-"" to 10-"? sec [DeMore and Dede (277)}, which corresponds to 10 10 100 vibrations during its lifetime. Arvis (46), on the other hand, photolyzed 1 tore of CO; at 1470 A and found, by infrared absorption, a product, CO», captured on a cooled LiF window. He estimates the lifetime of COS to be 0.04 sec, which is much longer than the estimated value of 10"! to 10" sec: Itis probable that CO, may be formed in sw on the cooled window rather than in the gas phase. Slanger (897) believes O is formed by the combination of COs 20, -+2C0; +O (EW) Asin the photolysis above 1672 A the ratio O,/CO is generally much less than 05, a value expected from material balance. Low values obtained at low CO, pressures indicate the loss of OVP) atoms on the walls (649, 897). At high CO, pressures Oy is formed from O("P) + O; “Oy, which partially explains the O2 deficiency [Loucks and Cvetanovic (649)] Slanger et al. (905) have measured the relative yield of CO production at several wavelengths in the range 1200 to 1500 A. The yields are 0.57 + 0.11, at 1216 A, 021 +007 at 1302 10 1306 A, 0.46 + 0.05 near 1390.4, and 0.58 4 006 at 1492 t0 1495 A, using Oo = 0.75 at 1470 A obtained by Inn (513). The authors have concluded that only the direct dissociation from an excited CO; produced by light absorption in the continuous portion of the absorption spectrum may contribute to the CO production. A good material balance (O,/CO = 0.5) was obtained in the Xe sensitized photolysis of CO at 1470 A (932, 933). Photolysis of CO; below 1200 A. The production of O(*S) is energetically possible below 1286 A C0; CO + O's) (V1-20) Lawrence (616) and Koyano et al. (584) have detected the production of O('S) by the emission at $577 A ('S-"D transition) in the entire region of absorption, 800 to 1220 A. The O('S) yicld increases to.a maximum at about 1150 Aand starts to decrease below 1080 A where the production of COlT1) begins. At 1048 A the O('S) quantum yield is 75 + 25% (616). ‘The CO,("E;) state must be responsible for the production of O('S), Below 1082 A the production of CON) is possible co, ¥ cow'n) + oP) (vii Lawrence (615) has confirmed the production of CO(u*M) from the emission of the Cameron bands (a*M- X'Z). The absolute yield of CO(a*M) has been measured in the absorption region 850 to 1100 A, The yield increases smoothly from threshold to « maximum of ahout 60% neur 900 A, Theproduction of metastable O atoms [O('S) and O('D)]} was detected by electron emission from metal surfaces when CO, was irradiated in the region 1030 to 1700 A [Welge and Gilpin (1036)]. By measuring the time- of-flight of metastable O atoms to reach a detector after flash photolysis, they have concluded that more than 50%, of dissociation leads to internally excited CO(X'E), Vibrationally excited COa%E*, d°A, and &E- are produced by excition of CO; with light of wavelengths below 923 A (552, 622). The vibrational population distributions are found to follow a Poisson formula. The quantum yield of CO, cq = 0.20 + 0.05, was obtained for the photolysis of CO, at $84 A (965). Emission spectra from the CO}(BE,;, A?M1,) states have been observed by Wanchop and Broida (1024) in the illumination of CO, at 584 A. VI-5.2. Stability of CO, in the Mars and Venus Atmosphere It is known that the main constituent of the atmospheres of Mars and Venus is CO;. The results of the photochemical studies of CO; in the laboratory indicate that CO, should be converted into CO and O; with solar radiation below 2275 A. The atmospheres of Mars and Venus should thus contain substantial amounts of CO and O,. Yet it has been observed that the mixing ratio of CO and Q, relative to CO, is only on the order of 10°* on Mars (677) and 10° * to 10° * on Venus (678). This unusual stability of CO; toward photolysis has been a mystery. McElroy and Donahue (677) and Parkinson and Hunten (798) have proposed an OH.-HO; cycle to catalytically recombine CO + O to form CO; OH +CO+CO, +H (v2) H +0, +CO,+HO, + CO, (1-23) O+HO;+OH +03, (vi-24) net CO +O CO; Hydroxyl radicals are produced by the photolysis of HzO, which is present to-an extent of 0.2% in the Mars and Venus atmosphere. Besides water, HCl, 4 minor constituent (6 x 10-7 mixing ratio) in the Venus atmosphere, may provide additional H atoms [McElroy et al. (678)] HASH +c Cl+ H+ HCL + H “het Hi = 2H More details are given in Section VIUI-3. $16. Carbonyl suipue (UC) The ground state is X'Z* (linear). The bond dissociation energies are dD for 12 40.03eV and De(O—CS) = 6.81 + 0. 13 eV ee re) ti A raviolet have 2550 A and is continuous. VI-6.1. Photodissociation in the Near Ultraviolet (1900 to 2550 A) a x s been found by Sidhu et al. (880) ‘The quantum yield of CO formation has been 0) to be 1.81 both at 2537 and 2288 A. The yield of CO has been reduced ion half (to a value of 0.9) by the addition of sufficient amounts of olefins. The primary process must be ocs co +S (V1-25) witha quantum yield of 09, Ithas been show by Gunning and Straus7 (430) that the reactions of S('D) with paraffins produce corresponding alky! mercaptans, It has been found (680) that 747 ofthe $ atoms. produced in {V1-25} form mercaptans with alkanes at 2288 A. Therefore, at this wavelengt! ocs% Co +S('D) $= 067 (VI-25a) ocs$Co+seP) 6 =024 (VI-25b) ‘The SCP,"D) atoms react with OCS to produce CO +S, [Langford and Oldershaw (600)] : SCP) + OCS + CO + S,005;) (vi-26) S('D) + OCS + CO +S"A,'E) kay (ian ‘The deactivation process S('D) + OCS + SCP) + OCS (E28) has been found to be minor. From the flash photolysis of OCS above 2200 A. Fowles et al. (371) have found indirect evidence that S2 in (VI-27) is either in the ‘A or "E metastable state. The metastable S, although not detected directly, may be collisionally deactivated to the ground state X*E,, whic was detected by optical absorption 8,(°4,'2) + M+S,00%,) + M (v2)4. ® °. 2 2300" 2300 R @ k 109. & o Fig. VI-S, (a) Absorption coefficients of OCS in the region 2100 to 2500 A. k is given its of atm" em™*, O°C, base e. From Ferro and Reuben (347), reprinted by per- ‘of The Chemical Society. (b) Absorption coeficents of OCS in the vacium et. ks given in units of atm” em”, O°C, base e.From Matsunaga and Watanabe wl (610), reprinted by permission. Copyright 1967 by the American Institute of Physi 26 VI-7. Carbon Disulfide (CS) 207 Breckenridge and Taube (144) have studied the photolysis of OCS + CS; and OCS + NO mixtures at 2288 and 2537 A. They have demonstrated that the primary yietd of production of S('D) [process VI-25a)] is 0.74 + 0.04 and 0.25 for SCP) production [process (Vi-25b)] in agreement with the results of Gunning and Strausz (430). The deactivation process [process {VI-28)] must be about one third that of the total reaction of S("D) with OCS in order to be consistent with their finding that $0% of the $ atoms formed in the primary process react as S(°P) (144), VI-6.2. Photodissociation in the Vacuum Ultraviolet Both SCP) and SU'S) atomic absorption lines have been observed in the vacuum ultraviolet photolysis of OCS by Donovan et al. (304, 305), indicating the occurrence of (VI-25b) and Ocs$CO + S('S) 2< 210A (vE-30) In spite of strong chemical evidence for the production of S('D), absorption lines of S(D) have not been found (304), presumably because of the rapid reaction with OCS molecules. Black et al. (114) have found that S(‘S) atoms are produced with a quantum yield of almost unity in the incident wavelength region 1420 to 1600 A, the COS("E") state presumably dissociating into CO + S('5), In the vacuum ultraviolet photolysis, the processes ocs cs +00) 2 < 18204 (Vita) ocsScs+0i'D) 2< 14104 (VI-31b) are energetically possible below the indicated wavelengths. However, Donovan (305) has found them to be of minor importance. Donovan et al 1304) also have found the S,(a'A) absorption bands in the vacuum ultraviolet flash photolysis of OCS. From the rate of increase of S,(a'A) they have concluded that the rate constant ky, is larger than 0.7 x 10°" em? molec! sec™!. As Sua) decays with time $,(XE,) starts to increase, indicating that $,(0E,) is formed by the collisional deactivation of S,(aA) [provess {VI-29)], Klemm et al. (574) have observed that the $ atom production in the primary process is more than 50 times as large as O atom production in the vacuum ultraviolet lash photolysis VI-7. CARBON DISULFIDE (CS,) The ground state is N'2, (linear). ‘The bond energy, DSC S$) ts A463 + YO14eV, corresponding tw the mealent wieclengty 27786 104 [Okal {769)), The absorption spectrin of CS, jn the near ultraviolet con two distinet regions af abserption. ame evening fiom 2a 1218 Photochemistry of Triatomic Molecules rs rN : ‘ta das bo we Tube Tate A A VI-6. (a) The absorption coefficients of CS, in the region 1200 to 1400 A. & is in units of atm~' cm", base e, 23°C. From Okabe (768), reprinted by permission. Copy- ight 1972 by the American Institute of Physics. (6) The absorption spectrum of CS, inthe region 2900 to 3400 A. Approximate absorption coefficients are given in nits of atm” em", base e, See Jungen et al. (554), and Treiber et al. (975), the other much stronger absorption extending from 1850 to 2300 A. The 3300 to 4300 A absorption bands have been assigned to the °Az—"E, transition by Douglas and Milton (320), The 2900 to 3200 A bands are very complex. Jungen et al. (554) have made a rotational and vibrational analysis from which they have concluded that the bands belong to the 'B;-'E transition, The 1850 to 23004 bands have been partially analyzed by Douglas and Zanon (321). The upper state is 'B,. Only a vibrational analysis has been made for the 1650 to 1750 A system (818). Two Rydberg series have been found by Price and Simpson (818) below 1400 A. The absorption coeffi cients in the region 1200 to 1400 A have been measured by Okabe (769) and are shown in Fig. VI-6a. The absorption spectrum in the region 2900 to 3400 A is shown in Fig. VI-6b. The photochemistry of CS; may be discussed above the incident wavelength 2778 A where the electronically excited state is important and below 2778 A where photodissociation may be important. VI-7.1. Photochemistry above 2778 A, Heicklen (451) was the first to observe fluorescence in the region 4200 to 6300 A when CS, was excited by incident light of wavelengths 2800 to 3600 A. Douglas (324) has measured a lifetime of 15 sec, which is somewhat longer than the 3 sec calculated from the integrated absorption coefficient, Brus (155) has measured the lifetime of the fluorescence excited by the 3371 A laser line, Two collision-free lifetimes, 2.9 + 0.3 and 17 + 2 psec, have been found, Jungen et al, (553) have studied the absorption spectrum near 3371 A and have assigned "47 and a triplet state as the two fluorescing states. FIR, Nitrous Oxide (N,O) 219 Lambert and Kimbell (596) have investigated quenching effects of various gases on fluorescence. No S atoms have been found in the photolysis in the region above 2300 A [deSorgo et al. (283)]. Instead, CS and S, have been found in the lash photolysis of CS, and N, mixtures. The proposed reactions cs cst (V1-32) CS$ + CS, +28 +8, (E33) where CS$ signifies an electronically excited state. VI-7.2. Photochemistry below 2778 A The photolysis of CS, + CzH« mixtures in the region 1950 to 2250 A have produced ethylene episulfide, an indication of S(°P) production [deSorgo cet al. (283)}. 1 csScs+sep) SCP) + CHa + HAC—CH, (v34) R55 In the fash photolysis of CS, in the region 1900 to 2100 A, Callear (166) has observed the production of vibrationally excited CS(X'E) and S(°P) but not S('D), Apparently CS and S(?P) are predissociated from the 'B, state in violation of the spin conservation rules because of the presence of heavy S atoms. In the vacuum ultraviolet photolysis a major primary process is 8, 8 C8(4'T) + SCP) (VL-35a) in apparent violation of the spin- conservation rules [Okabe (769)]. The dissociation below 1337 A apparently takes place from Rydberg states, Recently, Black et al. (118) have found the production of CS(a°N) in the 1250 to 1400 A region with high efficiencies hy 8, 8 CSM) + SCP) (VL-35b) The lifetime of CS(a*M1) is 16 + 3 msec. VI-8. NITROUS OXIDE (N,O) ‘The ground state is X'E* (linear), Absorption starts at about 2400 A. The absorption coefficients in the region 1080 to 2400 A have been measured by Zelikof etal. (1079), by Thompson et al, (967), and recently by Johnston and Selwyn (544). They are given in Figs. VI-Tu through VI-Te. Winter (1053) has assigned the 1809, 1455, and 1291 A absorption bands to the 'A, "I, 'Z* states respectively, on a theoretical basis. The bond dissociation energies are Do(N;--O) = 1.672 + 0.008 and Dy(N—NO) = 4.992 + 0,005 eV. Table250 © 200 = 150 2 100 aio ' 2300" as00 z a E 50 3 2 0 380 1410 144014701800 18301660 1550 1620, WAVELENGTH, A 2 . 3000 T T a ‘3 ea 4 zy °B 000 = - 1,0 a, E1000 | 4 5! 3 1200 eLiiiud Pui 1. 2 8 i600 12s 650 16751700 _1@00 19002000 = 600 4 g WAVELENGTH, A 5 o g + 4 Fig, IAT. (a) The absorption cross sections of NO in the region 2100 to 2500 A oLu=t ! tii T 1 11m units of cm mac", bate e, room temperature. From HS, Johnston and 6 2002301260 1290182050 BO Setwyn Geophys. Res. Lett. 2, 54) (1978). Reprinted with permission. Copyright by WAVELENGTH, A aphysical Union. (8)-(e) Absorption cocfficents of NO in the in nits of atm) emt", base er OC. From Zalikolf etal, (1079, permission. Copyright 1953 by the American Intute of Physi Fig. VIET. om)tem!) m ABSORPTION COEFFICIENT (AIM 1000 100 1080 100 *120.~—«M40—«16—*180 WAVELENGTH, A Fig. VI-7. (cont) Table VI-3a. Threshold ‘Warelengths (A) below Which Indicated Reactions are Energetically Possible in the is of NO No PD tS XIE Tais* 3407 2H AZ, 15K 12641031 BT, 13741128938 BPr, 12601050 RN “The threshold wavelength below which the, dissociation of NO into. NsiX"2) + OPPs energetically posible, 1200 1220 VI-8, Nitrous Oxide (N,O) 223 Vable VI-3b, Threshold lengths (A) below Which ied Reactions are Energetically Possible in the Photolysis of N20. DP XI 2519 16981439) Ast M192 970887 Br 795K RTT Vi-3a and VI-3b gives threshold wavelengths below which indicated reactions are energetically possible. VI-8.1. Photochemical Reactions ‘The photodecomposition products are known to be Nz, O2, NO, and NO; The formation of NO, from NO and O, is slow in the gas phase but the reaction 2NO + 0, -+2NO, appears to be accelerated when mixtures of NO +0, are repeatedly cooled to ~ 196°C and warmed again to room temperature (864). Primary Processes. Two primary processes, both spin-forbidden, arc energetically possible below 2500 A (VL-36) (VL-37) N,N, + 0CP) N,0“ NO + N(‘S) Ithas been found by Cvetanovie et al. (257) that O atoms produced from the photolysis of NO at 1849 and 2138 A are metastable O* [O(*D) or O('S)] toms, since the production of N3 by the reaction O* + N,O is suppressed by the addition of CO; or Xe, which quenches O* to nonreactive OF°?) ‘atoms, Subsequent studies suggest [sce Paraskevopoulos and Cvetanovic (791)] that, atleast in the region 1850 t0 2300 A, the O(*D) atoms are formed from the photolysis of NzO N,O +N, + O('D) “The possible occurrence of (VI-37) has been studied by Preston and Barr (816) Ifthe primary process is in part N,O NO +N (VE38)Photochemistry of Triatomic Molecules ve N atoms formed would react with !°NO added initially to NzO to form Ny N+ 'NO+?°N) +0 (vE-39) hie results of the photolysis of mixtures of NO + 1%, “NO at 2288, 2139, 1 1849 A show the production of less than 1.7",, 79Np, indicating that 1-37) is less than 2, of the primary process Secondary Processes, Two secondary processes may be proposed to plain the products Nz, NO, 3, and NO; O('D) + NJO-Nz +02 kao (VL-40) OU'D) + N30 + 2NO ha (Vial) he ratio Ayo/kay can be computed from ®p, and Oyo provided there is no «action between O, and NO. Kao _ 20, Ka «vi-42) lowever, because some O, and NO tend to react with each other to form 0; (of N,O,) during the analysis, the ratio kgg/ka, cannot be obtained liably from the measured ratio Of @o, to Myo Scott etal. (864) have measured instead the ratio of Nz to NO, produced ‘om the photolysis of Oy-N,O mixtures in the region where only Os bsorbs. From the reaction sequence 0, 50; + O('D) (Vi-43) OUD) + NON; +0, has (vi-44) 0('D) + N;0 + 2NO Kes (VES) NO +0;+NO; +0; (vF-46) sey have obtained the ratio, as NO molecules are all converted to NO, rolecules, hao Na] - = 0,99 4 0.06 ys [NO2] ~ The ratios obtained by various methods range from 0.6 [Greenberg and leicklen (419), Ghormley et al. (391), Simonaitis et al, (8R4)} to 1 {Greiner 423)]. I is most likely that the ratio is near unity since three independent niethods agree with each other (864). VI-8. Nitrous Oxide (N,O) 25 The photolysis of NO ubove 1850 A may be summarized as follows N,OEN, + 0('D) (vi-47) O('D) + N,0-+N; + Oy, how (V1-48) O('D) + N,0 + 2NO. kao (VE-49) Kan = key In spite of various energetically possible reactions given in Tables VI-%a and 3b, the quantum yields of the products are almost independent over the wavelength region studied except at 1236 A, suggesting that the above processes are predominant above 1470 A. The quantum yields of various products of NzO photolysis are given in Table VI_4 . Product VI-8. of Metastable Species by the Photolysis of NO Tables VI-3a and 3h shows that the photolysis above 1200 A can produce electronically excited atoms O('D,'S) N@D,?P) and molecules Na(A°E, BPM), Of these O('S) and N,(B7IT) are directly observed by the emission it ‘Table VI-4. Quantum Yields of Products in the N,O Photalysis Waele (Ay Product Quantum Yield 1236 Nz 1.18 + 003 (Ref, 426), 34 + 0.04 (Ref 293) 1470 1.40 + 0.06 (Refs. 426 and 1061), 1.4K (Ref. 292), 1.44 (Ref. 1080) 1849 (1.44) (Ret 1081) 2139 LST £011 (Ref 419) 123% 0,02 + BOT (Ref. 426),0.19 + 001 (Ret 1061) 1370 (OR + 003) (Ref, 1061), 015 + 0.01 (Ret 426) 05 (Ret. 1080) 1849 (~04) (Ref, 423) 209 0.059 (Ref 419), 1470 NO (O78 4 0.03) (Ret. 1061) 1¥49 OSL #008 (Ref 423) 1236 NO, 052 + 0.02 (Ref. 426) 1370, 0.78 +003 (Ref 1061), 0.74 + 005 (Ref. 426) NO 1236 145 4 004 Ref 426) 1370 1.76 + O08 (Ref. 426), (Ref. 1080) Kay ALTE O13) REE AY Nate: N49 A. y= My, + Pye +, 10, + NO foreach phot ay = LONE OOS ROL ABM ONO INsy Uy vtec Molecules 5977 A and by the first positive bands, respectively [Hampson and Okabe (436) Young etal, (1070, 1073)]. The production of O('D) atoms is suggested by the reactivity of O* atoms with N,O as described before. The NCD are responsible for the production of NO(B?T1) [Welge (1029) Young et al (112, 1071), Okabe (761)] by N@?D) + N,O ~ NO(B*T) +N, (VE-s0) The formation of Nz(AZ) is proposed from the observation of NO y bands by NAS) + NO + NOLA*E) +. Ny (Est) [Welge (1029), Okabe (761), Young et al. (1071, 1072)] and by electron emission due to collisions of Na(A7Z) on a metal surface (397), Recently, NCD,*P) atoms produced by the photolysis of N,O above 1050 A have been directly observed by absorption at 1493 and 1745 A, respectively (Husain et al, (502)). The quantum yields of metastable species at 1470 A estimated by Young et al. (1071) and Black et al. (113) are shown below Species Quantum Yield OVP) 0.08 0) 055 t's) 05,01 (Ref, 680) NCD) on N4°2) 0.08 Recently quantum yields of O('S) from NzO have been determined as a fanction of incident wavelength. The yield is near unity at 1290 A [McEwan ct al. (680), Black et al.(113)]. Because the photolysis of N,O is a convenient source for the production of O('S), N@D), N,(A°5), and Nx(B°T), their Quenching rates by many gases have been measured by monitoring emissions produced by the photolysis of NzO and quenching gas mixtures, Chamber. tain and Simons (203) believe that in the region 1400 to 1550 A'NO is produced mostly from two reactions O('D) + N,0 + 2NO (VE-S2) NAA*E) + N,O+N; +N +NO. (ViS3) VI-8.3. NO in the Upper Atmosphere The concentration of NzO in the lower stratosphere is about 0.2 ppm (405) ‘The reaction of O('D) with NzO to produce NO is considered by Nicolet FLY, Nitrogen Dioxide (Wy) 221 ind Peetermans (7392) to be an important source of NO in the stratosphere. O('D) + N,0 + 2NO (Visa) See Section VIII- 2.2 for further discussion. DIOXIDE (NO,) VL-9, NITROGE! The ground state is X24, with an O--N-—O angle of 134.1° (16). pecs 0) = 3.118 4 001 eV (28). The absorption spectrum of NO, in the near ultraviolet and visible is extremely complex and for the most ps ents of (a) 1100 to 1600 A region: absorption coeffi- Sea gvnineniotatm enn 0°, erm Naya et (3) (0) 10 ve nits of atm" ‘em™", base ¢, 0°C. From Nakayama et a to 2700 A region: k is given in units of atm’ Ee Bo Ten sean (731). (c) 2500 to 5000 A region: Serco Seno 7 a he a ee Tor fmt atm") base - Reprinted with permission, Copyright 1982 and 1989 by the [American Institute of Physics. ‘lent & i given in univo0gy ‘+> —+—— 1700 1200 100 A roo k4 5 200 2do0 2400 2600 o vo Te TT Tk Fig. VI-8. (cont) ne VI-9. Nitrogen Dioxide (NO;) 229 apparent regularity in rotational and vibrational structure. Electronic states identified are EE, in the region 1350 to 1650 A by Ritchie and Walsh (832), BEB, at 2491 A by Ritchie et al, (831), and AB, or 2M, in the region 3700 t0 4600 A by Douglas and Huber (322), Recently, Hardwick and Brand (442) assigned the origin of the transition A'?B,-XA, at 14.743.5 cm”! (1.828 eV). Brand et al. (132) have determined the 0-0 transition of the A?B,-X?A, system at 11,956 em”! (1.482 eV), ‘The rotational analysis of the 8000 to 9000 A band system, A2By-X?4,, has been made by Brand et al. (133). The A#B, state is severely perturbed by the X74, state. The 7B, state has an O-N O bond angle of 102° [Gillispie et al. (395)]. Smalley et al. (909) have measured the fluorescence excitation spectrum of the cooled NOs in the region $708 to 6708 A. The *B, state isthe only upper state inthis region. The absorption coefficients in the vacuum ultraviolet, near ultraviolet, and visible regions have been measured by Nakayama et al. (731) and by Hall and Blacet (431) and are given in Figs. VI. 8 through VI-Se. The absorption coefficients in the region 1850 to 4100 A at higher resolution have recently been measured by Bass et al, (72), The electronic energies, potential energy surfaces, and oscillator strengths of various upper states have been calculated by Fink (354, 355), Gangi and Burnelle (384, 385), and Gillispie et al. 395), Nitrogen dioxide is one of a few simple molecules in which the primary quantum yield near the dissociation limit (3980 A) has been measured nearly continuously as a function of incident wavelength, The energetics of photodissociation is given in Table VI-5. The thermochemical threshold at 0K for the reaction, NO, + NO + O(*P), corresponds to the incident wavelength 3978 A, which nearly coincides with the wavelength 3979 + 1 A below which ‘Table VI~S, Theeshould Wavelengths (A) Below Which Indicated Reactions are Energetically Possible in NO, Photolysis Ss Noo 4e Xen 397R 491497 ast 14821174 970 Notes, NO +N 4 Op: Al mot! corresponding to 2781 A. The threshold wavelength below which the disociation of NO, into NOU) and OUP} s cnergetcaly posible 039 keal490 nowwchemstey of truatomae Molecules Totational structure of the NO; absorption spectrum becomes diffuse [Douglas and Huber (322)]. Even above 3980 A internal energy is known to contribute to dissociation [Pits etal. (810), Jones and Bayes (550)], Above 3980 A it has been known that NO» fluoresces strongly in the visible region The lifetime, the spectral analysis, and quenching properties ofthe Nuorescing. state have been studied by many workers. The photodissociation of NO, may be conveniently discussed above and below 3980 A VI-9.1, Photodissociation above 3980 A The primary quantum yield of NO, dissociation obtained from Mp, falls off rapidly above 3980 A and is 0.005 at 4358 A [Pitts et al. (810)}. Since the extent of isotopic scrambling of O, by illuminating mixtures of NO, and!" O; closely follows the quantum yield of NO production, there is litle doubt that © atoms are formed by direct dissociation of NO, at four wavelengths tested, 3660, 4020, 4060, and 4120 A [Jones and Bayes (550)] The falloff curve of the quantum yield is explained by the contribution of the internal (mostly rotational) energy to supplement the incident photon energy (550,810), (sec Section 1-43 for details), Above 4358 A a small (~001) but significant yield of NO was observed. which is attributed to reactions of electronically excited NO, (NO) by Jones and Bayes (550) NOf + NO; +2NO +0, (VES5) NO$ + NO, + NO, +NO (VI-56) Creel and Ross (251) have studied the NO; photolysis in the region 4580 to 6300 A. They also conclude the occurrence of (VI-55) by measuring the Production of O;. Hakala etal. (433) have found the production of O, from NO, by irradiation with the 6943 A laser that has insufficient enesgy to induce dissociation, Since the O production was dependent on the square of the laser intensity, they postulated the consecutive absorption oftwo photons VI-9.2. Photodissociation below 3980 A The electronically excited NO, formed by absorption of light wavelengths below 3980 A must have q lifetime on the order of 10” '? sec, since the absorption spectrum shows diffuse rotational structure (but not the vibratio structure) [Douglas and Huber (322)]. Experimentally, a lifetime on the order of 5 x 10°? sec is obtained from the Photolysis yield of NO, at various added N, pressures in the region 3100 to 4100 A [Gaedtke etal (378, 379)] Busch and Wilson (162, 163) irradiated a molecular beam of NO; with a pulsed laser of wavelength 3471 A and measured the flight times of the ben ow vay 230 1 fragments toa mass spectrometer-detector. They obtained Intrnation om the energy parionng between transational nd itr degrees of freedom ofthe eclling O and NO fragments. When a polarized light souree was used, the angular distribution of recoiled © atoms peaks along the diretion of the electri vector ofthe polarized ght. This ndeates the predominant state produced by absorption at 3471 As Bs However this assignment is not in accord with that of *B, by a rotational analysis (322) [se also Section 11-5} The main photochemical reactions of NO> in the region 2439 to 3978 A are the production of O(?P) atoms and the rapi reaction of © atoms with NO NO, “NO + OPP) (VE-s7) OCP)+NO;+NO+O, — ksy (VES8) yy = 9.1 x 10>? em? molec”! sec” (Ref 9) ‘rom the mechanism the quantum yield of the primary process is equal to the {jam ytd of Oy production (Og) or onc half of NO production [x] It has been shown by several workers [Pitts et al. (810), Ford and Jafle He Jones and Bayes (550) that Op, or} is near unity at 3130 A and gradually decreases the incident wavelength increases, Theres some indication that another electronically exited state maybe formed by light absorption in the region 3300 to 5900 A to an extent of several percent (372, $49). This st ss being sulficiently long-lived is capable of transetig ts eletronic energy to ; to produce ©,(°A) [Jones and Bayes (548, 549}, Frankiewicz and Berry 372) OPN 228 thee diseciaton processes arcenergtily possible NO; NO + OP) (VI-59) NO, 5 NO + 0('D) (VI-60) NO, SN +0, (VI-61) xpected Process (VI-61) contributes little, if any, since NzO_and Np, the expect products from the reaction of N with NOs, are minor products in NOz photolysis at 2288 A [Preston and Cvetanovic (815)] se “ Since isotopic scrambling of Os (production of 0, and $40, mixtures has been seen inthe photolysis of mixtures of NO, C/O, at 2288 A bat not at 2537 or 3660 A, Preston and Cvetanovic (815) have concluded the production of O('D) from (VI-60) followed by the reactions 0('D) + C0; +CO; + #0 LE) 180 4 NO; NO +0; °” wren232 Photochemistry of Triatomic Molecules They estimated about 40% Ol" Dis produced in the primary processes at 2048 A Table VI-S shows that the dissociation process, NO, -* NO + O('D) takes place energetically below 2439 A. Uselman and Lee (985) have me sured the production of O('D) as a function of incident wavelength near 2439 A. They have found that the contribution of rotational energy to dissociation is insignificant near the second threshold in contrast to the case near the first threshold at 3980 A where the contribution of rotational energy is substantial. They attribute the lack of rotational contribution to the presence of large rotational barriers at high J values in the excited state (987). The quantum yield of O('D) production increases to a plateau of about 0.5 + 0.1 towards shorter wavelengths, indicating that at least two processes, (VI-59) and (VI-60), occur concurrently below the second threshold wavelength. I-93, Photodissociation in the Vacuum Ultravioet Welge (1030) has observed that electronically excited NO in the A?" and B'NT states was produced from NO, by radiation with the Kr (1165, 1236 A) and Xe (1236 A) lines. Lenzi and Okabe (625) have measured a fluorescence yield of about 2°, at 1216 A. The production of excited states other than APE" and BPIT has been suggested. VI-9.4. Fluorescence When NO, is irradiated with light of wavelengths above 3980 A, fluorescence from NO, has been observed. The fluorescence spectrum lies in the region from the exciting wavelength to above 7500 A. Many rotational and vibrational lines are superimposed on a continuum. The collision-ree lifetime, measured by Neuberger and Duncan (733), is 44 yesee when excited at 4358 A while the mean life calculated from the integrated absorption coelicient is about 0.26 sec. This diserepancy between the measured lifetime and the lifetime calculated from the integrated absorption coeflicient has been explained by Douglas (324) (see Section II-2.1)on the basis ofthe interaction of the excited and the ground state, Keyser et al, (562) have found no significant variation of lifetime of fluorescence in the region of absorption 4360 10 6000 A, indicating that there is probably only one excited state. On the other ind, Abe (35)and Abe et al.(34, 36) have concluded that both the 7B, and?B, ates are responsible for fluorescence in the visible region of the absorption spectrum, The excited state formed by the 4420 A tine is ?B, with a lifetime of 46 psec [Schwartz and Senum (863)}, Stevens et a. (926) have found evidence of the two excited states, 23, 2B, in the 5934 (0 5940 A region of absorption from the rotational analysis of the fluorescence spectra and the lifetime of VIM, Nitrogen Dioxide (NO;) 133 Nuorescence. They have concluded that the *B, has a lifetime of 30 + 5 see and the 7B, has a lifetime of 115 + 10 psec, Some rotational levels of the NO, electronic state in the visible region appear to be unperturbed by other states, since the lifetime of the fluorescence from these levels is indeed very short (0.5~3.7 psec) (847), approaching that predicted from the integrated absorption coefficient. These levels have been found in the region 4544 to 4530 A by Sackett and Yardley (847) and by Solarz and Levy (920) at 4880 A. ‘A more recent work by Paech et al. (789) on the collision-free lifetimes of NO, excited by a tunable laser near 4880 and 5145 A states that although only a single level is excited, three different lifetimes of fluorescence, 3, 28, and 75 yisec, have been observed. The results lead them to conclude that the initially formed *B, state crosses over rapidly to another state, *B,, with higher level density. The ?B, state can have two different lifetimes (28 and 75 11sec), depending on the extent of interaction with the ground state. The short life observed. 3 sec, is determined primarily by the rate ofinternal conversion from the 7B, to 7B, state. The results of some reported collision-free fluorescence lifetimes are given in Table VI-6a. ‘The NO, fluorescence is quenched by almost all gases. However, the usual Stern-Voimer plot, assuming one excited state that may either radiate or be collisionally deactivated to the ground state, shows a linear relationship for self-quenching only at a given exciting and Muoiesceuce wavelength Tht i, the self-quenching constant a, defined by (II-1) is a function of both the exciting and fluorescence wavelength. Furthermore, quenching by foreign gases, He, Nz, and O2 does not follow the linear relationship given by (II-1) (Myers et al. (729), Braslavsky and Heicklen (136)}. The fluorescence spectrum shows a red shift at higher pressures (729), indicating that quenching is a multistep process with consecutive vibrational ‘Table VI-6a. Radiative Lifetime of the Electronically Excited NO Lifetime Exclting Light (ise) elength (8) Method Ret 44 4358 Pulsed Light 733 5545 4360 6000 Phase Shift 562 55°90 3980-6000 Phase Shift 862 4246 4420,4510, 4840 Pulsed Light 850 OS 4545-4550 Pulsed Light 847 62°75 4515 4605 Pulsed Light ax * Observed nly at several exeitation wavelength2364 Photochemistry of Triatomic Molecules deexcitation of NOY and radiation from each of several vibrational levels When the fluorescence wavelength is farther apart from the exciting wavelength, the quenching constant decreases rapidly. Keyser et al. (562) have concluded that the dependence of the quenching constant ay on A¥ (the difference Of the wavenumber of the exciting and Muorescing light) is best explained by assuming a single electronically excited state of a lifetime of about 50 ysec, an efficient vibrational relaxation (almost unit efficiency}, and slow electronic quenching (1 in 100 collisions), The vibrational quantum transferred per quenching collision is 1000 + 500 cm” !. Some quenching constants at the 4358 A excitation and the fluorescence wavlengths above 4600 A are given in Table VI-6b [Myers etal. (729)} ‘The Muorescence yield as a function of incident wavelength has been measured by Lee and Uselman (619), The yield starts to increase from 0 at 3979 A o nearly 100%, above 4150 A. The decrease of the yield below 4150 A isattributed to an increase of predissociation supplemented by the rotational energy of the molecule, since incident light of wavelengths above 3979 A does not have sufficient energy to dissociate the molecule at 0°K (550, 619) Useiman and Lee (986) have observed that the fuorescence lifetime is constant (70 psec) inthe absorption region 3980 to 4208 A. From the results they suggest two kinds of excited NO,, one fluoresces with a constant lifetime and the other predissociates within less than 100 nsec ‘The fluorescence from NO excited by the 4416 and 4880 A lines is used for measuring NO; concentrations in air in the parts per billion range (388) Table VI-6b, Quenching Constants,” ‘44 of NO, at the 4358 A Excitation and the Fluorescence Wavelength Near 500 A [by Myers et Quenching Quenching Constant. — Quenching Constant ay(lore") Gas ay torr) He » 82 Ar 30 v1 Ni cn 100 oO; 48 105 Hy 62 155 NO. 2 160, H,0 280 "The quenching constant is ku/ky defined in Section M12 where fyb the quenching rate constant in torr sce! and [pis the Ruorescence decay rate im sec Gate Fig. VI-9. Concentration-time history of reac tants and some products in the photooxidation of CJHg. Mixtures of C,Hy + NO + NO; fir wereleradiated by simulated sunlight in smog, chamber. Reprinted with permission from Niki, E-E. Daby, and B. Weinstock, in Photo- chemical Sriog and Ozone Reactions, RF. o Gould, Ed., American Chemical Society, Was t ington, D. C. Copyright by the American Chem riuccuiny eal Society, 1972. VI-9.5. Nitrogen Dioxide in the Atmosphere It has been recognized that NO, plays a central role in the formation ot photochemical air pollution [see Niki et al. (743), p. 16], Absorption «! sunlight by NO, in the spectral region 3000 to 3890 A leads to the produetior of O atoms, By the combination of © atoms with Oz, 5 is formed. The reactions of © atoms, OH radicals, and Oy with hydrocarbons (main! olefins) initiate photochemical air pollution. Figure VI-9 shows a typi time history of the concentrations of reactants and products when mixture of C,H, NO, and NO, in air were irradiated by simulated sunlight in smog chamber (743). The concentrations of CH and NO decrease wit irradiation time while NO, and an oxidation product of CsH,,acetaldehy< start to increase. Ata later time, O, and PAN (peroxyacetylnitrate) start | appear when the NO, concentration reaches a maximum, ‘According to Bufalini (158) Oa('A) produced partially by energy trans! from the electronically excited NO, to Oz molecules, postulated by Frank wicz and Berry (3721), does not contribute to air pollution. Further discussion of photochemical air pollution is given in Sect ull VI-10, NITROSYL HALIDES VI-10.1, Nitrosyl Chloride (NOC) ‘The ground state NOCT is bent with an O- N~ Clangle of 116”. D> Cl) = 1.61 + 0.01 cV (28). Absorption starts at about 6500 A. The absorpt236 Photochemistry of Triatomic Molecules i, is € 10. ry ook 3060 ‘aco Fig. VI-10, Absorption coefficients of NOCI in the visible and ultraviolet region. € is “ain units of L mol" em”, base 10, room temperature. [Goodeve and Katz (411, Fevised by Ballash and Armstrong (58) reprinted by permission of Pergamon Press. coefficients in the region 1900 to 4000 A have recently been measured by Illics and Takues (508). The absorption coef 6500 A have been measured by Goodeve and Katz (411) and more recently by Ballash and Armstrong (58). They are shown in Fig, VI-10. The absorption coeflicients in the region 1100 to 2000 A have been meusured by Lenzi and ‘Okabe (625) and are shown in Fig, VI-11 Photochemistry. The quantum yield of NOCI decomposition is 2 over the incident wavelength region from 3650 to 6300 A [Kistiakowsky (570)] and at 2537 A [Wayne (1025)]. Since the absorption spectrum in this region is continuous, the photochemical process must be Nocl$ NO + Cl (V1-64) CLE NOCI4NO+Ch hes (VL-65) jents in the region 100 16 fand Okabe (625)), reprinted with pe mmission of Verlag Chemie, VIN, Ozone (Oy) 231 The rate constant, kys = 30.5 x 10-1! em? molec”! has been measured by Clyne and Cruse (221). The photodissociation of NOCI at 2471 A has been studied by Busch and Wilson (164) using a polarized monochromatic pulsed laser. They concluded that the photodissociation ‘eccurs from a state with A” symmetry since dissociation into NO + Cl is induced by light polarized in the molecular plane. The excess energy beyond that required to break the N--Cl bond goes predominantly (70?,) into the translational energy of the recoiling fragments. Basco and Norrish (63) have observed vibrationally excited NO up to v= 11 in the flash photolysis of NOCin the n jolet. The mec ultra ism of production is either directly NOC NOUX?T.e" <1) + CL (VI-66) or through NOT) Nocl# NO@M) + Cl (V1-67) NO(T) + M+ NOT, p> 0)+M (vE-68) Equation (VI-67) involves a crossover from the initially formed singlet to a repulsive triplet state of NOCI The photolysis of NOCI in the vacuum ultraviolet produces NO(A?E "0° = 0,1,2) [Welge (1030)] and possibly other excited states of NO [Lenzi and Okabe (625)}, The Muorescence yield near 1500 A is about 4", (625). VI-10.2. Nitrosyl Fluoride (NOF) The ground state NOF is X'4" with an O—N-—F DON —F) = 238 + 003 eV (28). ‘The absorption spectrum in the near ultraviolet lies in the region 2600 to 3350 A (16) with some vibrational structure Photolysis with an unfiltered medium pressure Hg lamp has been made in the presence of ethylene and other hydrocarbons. The photolysis rate decreased when inert gases were added, indicating the formation of electronically excited NOF (364), which may decompose or be deactivated by an added gas. le of 110° (16). VI-II, OZONE (0,) Ozone is a bent molecule with an angle of 1168". The bond energy D{O- O,)is 1.05 + 0.02 eV (28). Absorption of light starts at about 9000 A. The absorption in the ultraviolet and visible regions consists of the Hartley bands (2000 to 3200 A), the Huggins bands (3000 t0 3600 A), and the Chappuis bands (4400 10 $500 A), The absorption coefficients of these bands ste given in Figs. VI Laand VI 12b, Figufe VI-12c shows the absorption coeflicients in the vacuum ultraviolet region.A 6. k 2. °. at00 ‘600 obo) A @ ig. VI-I2. (a)Absorption coefficients of Oy Huggins bands (3000 to 3600 A) and ‘Chappuis bands (4400 to 8500 A): & (atm=" em~"), 0 C, base 10. From Griggs (425), per (8) Absorption coefticients of O, Hartley bands (2000 to 3000 A), k is in unit em”, 0°C, base 10. From Griggs (425), reprinted by permission. Copyright 1968 by the American Institute of Physics. (c) Absorption coefficients of O, in the region 1000 {0 2200 A. kis in units of (atm~* em”'), O°C, base e. From Tanaka etal, (961), reprinted by permission. Copyright 1953 by the American Institute of Physics. 238 120. 80. 40. °. 2000 2500 3000 K o 100 " k 10 1 1000) E 2do0 A wo Fig. VI-12. (cont) Since the absorption spectra are diffuse over the entire spectral region. no assignments of transitions have been made from the analyses of the spectra. Hay and Goddard (449) have recently assigned the Hartley bands to @ transition 'B,-'A, (origin at 3515 A) and the Chappuis bands to BA, ‘An excellent review on Oy photochemistry up to 1971 has been given recently by Schiff (857). Ozone dissociates by absorption of light of wavelengths below 9000 A. Table VI-7 gives the threshold wavelengths below240 Photochemistry of Triatomie Molecules which designated photochemical processes are energetically possible. We discuss. photodissociation processes separately for the three absorption regions in the visible and near ultraviolet. VI-IL1. Photodissociation in the Chappuis Bands (4400 to 8500 A) “The quantum yield of O disappearance by absorption of re light (~ 6000 A) is 2 (193). The result is best explained by the primary process 0, SOP) + 04072) (V1-69) followed by OPP) +0520; kro (vi-70) " c 1y/RT] em? molec”! see”! (265). kyo = 2.x 10° exp [ (4522 cal mol” !)/RT] em? molec t Although the production of O,("A) is energetically possible betow 6110 A {sce Table VI-7) by a spin-forbidden process, there is no evidence that 0,4") is produced, since the overall quantum yield of ozone decomposition remains the same throughout the entire region. [If O,('A) is produced for 7 < 6110 A. 9, would increase from 2 t0 4, See the following section. ] VI-I1.2. Photodissociation in the Huggins Bands (3000 to 3600 A) The quantum yield of © decomposition at 3340 A is 4 (196, 546), indicating that one of the products must be an excited species capable of decomposing Oy further, Castellano and Schumacher (196) have found no effect on the quantum yield even when 500 torr of Nz was added to 50 torr of Oy. Ifthe primary process is 0,5 0('D) + OLX'E) (VE-Tla) itis known, as is described later, that the O(1D) atom reaction with Oy is OD) +O, +O; + 200°P) (VE-TIby ‘Table VI-7. Wavelength Thresholds (A) below ¥ Indicated Reactions are Energetically Possible (0, Photolysis 0/0, OR 2p TBO GIO 4630 2001730, DIG 3100 265016801360 's 702000 180012901090 “The thresholel wavelength below whieh the dlissocat Oy into OPE, ) + OCP} is eneepeticlly possible VIII. Ozone (Oy) 24b The addition of N; should quench O(*D) to OCP) quite efficiently (Section IV-4.1), Therefore, itis expected that the quantum yield is reduced from 4 (© 2 when N, is added, Since no change of quantum yield is found, the excited species must be either O,('A) or O3('). It is not apparent from the effect of N; alone which species is formed. The primary process of the Oy photolysis at 3340 A must be a spin forbidden process 0, 8 OCP) + O,E or 'A) (vi-72) followed by OCP) + 0, +0, + 02 (VL-73) and OYE or 'A) + Os +O; + 0; + OFP) (vi-74) From the mechanism the overall quantum yicld of Oy decomposition is 4. Another process, Os "8 O('D) + O('4), becomes important with light of wavelengths below 3200 A. The process is described below. VI-11.3. Photodissociation in the Hartley Bands (2000 to 3200 A) The Primary Process. The primary process of Oy photolysis in the Hartley bands appears to have heen wel estublished. The primary molecular Product has recenily been directly identified as O,("A) by detecting the infrared atmospheric band at 12,700 A during the 2537 A photolysis (547). Jones and Wayne (547) obtained a quantum yield of nearly unity (0.9 + 0.2) for the O,('A) production. The O,('A) produced by Oy photolysis was also detected by its absorption in the vacuum ultraviolet (311) (see Section V6.2), although an carlier study (516) failed to detect the atmospheric band «mission from the O,('A). The electronic state corresponding to the Hartley bands is probably 'B,, which can dissociate by a spin-allowed process into 0,('A) + O('D) below 3100 A 04'B,) O"A) + OF'D) (VI-75) ‘The direct detection of O('D) may be made either by absorption at 1152 A cr emission at 6300 A immediately after Mash photolysis of O, (see Table A 2 The detection of O('D) by the emission at 6300 A would be extremely ifficult because the emission life is about 150 sec (32). Even at a pressure of I mtorr of O, each OL'D) atom would undergo about 10° collisions with ©, molecules during its lifetime. Consequently, the emission intensity would te reduced by a million times by collision quenching. In spite of the diffcul- ‘tes, Gilpin ct al. (398) have succeeded in following the decay of the extremely244 rnowenemistey of irtatome biolecuies weak emission at 6300 A by accumulating signals from 600 flashes. The decay rate of O('D) is governed by the reaction rate of O(*D) with O, from which Gilpin et al. obtained a rate constant of 25 +1 x 10°! cm? molec”! see~!, which corresponds to almost unit collision efficiency. They have shown also that the production of ©,(') in the primary process is not more than 5% although the process is energetically allowed below 2660 A (sce Table VI-7) Secondary Processes. Snelling et al. (917) followed the consumption of © as a function of time after flash photolysis of Os. The results show that the ozone consumption occurs in two distinct stages, a very fast process (less than 50 ysec) followed by a slow process lasting many milliseconds, The fast process is attributed to the reaction O('D) + O10; + 20 oF 20, (VI-76) Giachardi and Wayne (392), using a flow system, have found that the yield of Os decomposition at the end of the fast provess in a He-Oy system is twice as large as that in a Na~ O, system. The results agree with the observation by Snelling et al. (917), The decrease of the Os consumption in the Ns-Oy system is attributed to an efficient quenching of O('D) by N, to OCP) The slow consumption process would involve the reactions OPP) + Os +202 (VI-77) O,('4) + 0,420; +0 (vi-78) ‘The reaction of O("D), produced in the primary process, with O, would be (392, 1027) either O('D) + 0, -+208P) + 0; (v7) or OUD) + Oy +20, (VI-80) The reaction could aiso produce vibrationally excited O, (55, 361, 1027) which does not appear to induce further decomposition of O, [Fitzsimmons and Bair (361)}. Giachardi and Wayne (392) have estimated the occurrence of (VI-79) to be one third the total reactive collisions of O('D) with Oy, Another estimate of over 90%, for (VI-79) is given by Webster and Bait (1027) and Bair et al. (55) The primary molecular product. O.('A), process ts further with Oy by the 0,('A) + Oy + OPP) + 20, (VESI) followed by OP) + Os +20; (vi-82) The maximum quantum yield of ozone decomposition, o,. has been measured to be 4 (546), 5.5 (640), and 6 (998). Norrish and Wayne (748) found that 4, increases at higher O, pressures, although no pressure effect on g,has been found by others (640, 998). This discrepancy is probably due to experimental conditions such as the presence of impurities and the walls, which would deactivate excited species. The quantum yield, ®o, = 6, can be explained on the basis of (VI-75). (VE-79), (VI-81), and (VI-82), while ©_o, = 4-can be explaned on the basis of (VI-75) and (VI-80) through (VI-82). The intermediate value ®o, = 5.5 indicates (VI-75) and (VI-79) through (VI-82). Thus, one obtains the various ‘values of the quantum yield of Oy decomposition ranging from 4 to 6 by changing the ratio of (VI-79) to (VI-80). Instead of the reactions (VI-79) and (VI-80) for the O('D) with O, reaction, some workers (998, 1026) propose the reaction O('D) + O,+ Of +0; (VL-83) followed by Of + O; + OUP) + 20, (VI-84) where Of is an unspecified excited state of O,. The sequence (VI-75), (VII), (VI-R2), (VI-83), and (VI-84) gives © 0, = 6 The photolysis at 330A gives conflicting results. Castellano and Schumacher (194, 195) obtained 0, = 6 and concluded that the same primary process [process (VI-75)] proposed for the 2537 photolysis ‘occurs at 3130 A with unit quantum efficiency. Lin and DeMore (637) have irradiated mixtures of ©, and isobutane with monochromatic light of wavelengths from 2750 to 3340 A at —40 C The bandwidth was 16 A. The relative quantum yields of O("D) production were obtained from the yield of isobutyl alcohol, a product of the reaction O('D)+ isobutane. The results are shown in Fig. VI~13. The {quantum yields are constant below 3000 A and show a sharp cutoff at 3080 A. the thermochemical threshold wavelength for the production of O('D) + 0,0’), ‘According to Moortgat and Warneck (717) the process 0; 8 0,('4) + O('D) (VEXS) becomes important below the incident wavelength 3200 A at room tempers ture, The thermochemical threshold at 0°K for (VI-85) is 3100 A. The quantum yield of O('D) production at 3130 A at room temperature is about 0.3 [Moortgat and Warneck (717), Kuis et al (591)] and it decreases at lower temperatures (591) [Lin and DeMore (637) Kajimoto and Cvetanovic (555)] The quantum yield of O('D) production estimated by other workers 15° 0.1 (546) and 0.5 (887) at 3130 A.244 Photochemistry of Triatomic Molecules 2doo 360) 3800 a Fig, VI-13. The quantem yield of O('D) from O, photolysis at —40°C as a function of incident wavelength. Band ih 16. From Lin and DeMore (637), reprinted by permission of Elsevier Sequoia, A, The ©, =6 obtained by Castellano and Schumacher (194, 195) at 3130 A indicates yoy to be unity. To be consistent with other results, the clfective wavelengths for Oy photolysis in their experiment must be below 3100 A. At room temperature internal energy of O, contributes to dissociation at 3130 A, See p. 22. VI-IL.4. Photolysis of O, in the Presence of Other Gases Oy + H,O system. Quantum yields of O, photodecomposition at 2537 A in the presence of HO are much larger than those of pure O,. They increase linearly with Py yo (640, 749). The results are interpreted on the basis ofthe following chain mechanism by 05S O('D) + OA) (V1-86) O('D) + H,0 + 20H (VI-87) OH + 0,+HO, + O, (V1-88) HO, + 0, OH +20, (vi-89) However, there is no direct evidence for the chain reactions (VI-R8) sind (VE-89}, DeMore (275) presents evidence that (VI-89) does not occur at 87°K VIII, Ozone (O;) 245 He also proposed the alternative chain mechanism, O('D) + H,0 + OH < 2)+ OH (V-90) OH > 1) +O, +H + 20, (vist) H + 0) + OH <9) +O; (VI-92) where v indicates the vibrational quantum number of OH radicals, Since the reaction OH + 0, +H + 20, is endothermic by 8 keal mol”', OH must be vibrationally excited (0 2 1) for the reaction to be energetically feasible. The reaction H + Oy is known to produce OH in v < 9 (206). Reaetion (VI-90) has been observed to yield OH in » = 0,1, and 2 (335), However, (VI-91) bus not been verified. The chain reaction has not been observed in the flash photolysis of O,-HzO mixtures (109, 370, 609). On he other hand Simonaitis and Heicklen (889) have found that the photolysis of Oy H,O mixtures at 2537 A leads to the chain decomposition of Oy. They nave found that the addition of O, does not inhibit the chain appreciably. Since O, reacts with H to form HO, they have concluded that the sequence IVI-91), (VI-92), which involves the HOH chain, is not operative in the Oy-HO photolysis. The sequence (VI-88), (VI-¥8), which is the OH—HO, chain, is favored [see also DeMore and Tschuikow-Roux (280)). O,-RH Sistem, Norrish and Wayne (749) have studied the O, RH system where RH = H,0,H,,CH,, and HCL. In each case the quantum yield of ©, decomposition is greater than that for pure Oy photolysis, The results are explained by the following mechanism 0, 274.0, + 0D) (vi-93) O('D) + RH+OH +R (vi-94) OH +05 + HO, +0, (vss) HO, + 0, +OH +20, (Vi-96) R +0, +RO+0; (vis) VI-AL.S. Ozone in the Atmosphere Because of absorption by O, in the stratosphere, solar ultraviolet radiation reaching the surface of the earth is limited to wavelengths above about 3000 A. Since the possible partial destruction of the ozone layer by the injection of pollutants such as NO,(NO and NO,) and chlorofluoromethanes would induce global temperature changes and have an adverse health elfect, such aan increase of skin cancer, the subject has been studied by many workersevs nviuenemustry of Hrtaronuc Molecules and is further discussed in Section VIII-2. An extensive review of 0, and O atom reactions with hydrogen, nitrogen, and chlorine compounds in the stratosphere is given by Nicolet (740) and by Diitsch (328). Briefly, the four following reactions control the ozone profile in the stratosphere, by 0,80+0 — 7<2400A (VE-98) O0+0,4+M+0,;+M M=N,,0, (VI-99) 0 +0, +20, Koo (E100) O,8040, 2<11800A (VE-101) The equilibrium concentration of ozone is established with a maximum at an altitude of about 25 km, depending on the intensity of the solar flux, the rates of formation [processes (VI-98) and (VI-99)] and those of destruction of ozone [processes (VI-100) and (VI-101)]. The concentration profile of ozone as a function of altitude is given in Fig. VI-14. It has been recognized, however, that the four reactions (VI-98) to (VI-101) are not sufficient to account for the global ozone balance. About 80%, of the ozone produced by sunlight must be destroyed by reactions other than those proposed by (Chapman, Johnston (543) and others have proposed that the most important catalytic cycle responsible for ozone destruction is a NO-NO, cycle NO +0,~+NO; +0; (vI-102) O+NO;+NO+0, his (VE-103) net O +O, +20; 6. Fig. Vi-14, Orone concentration (enotee em") as a function of altitude, ie o Hg From Randhawa. (822), reprinted by 6 permission of Birkiniuser Verla , (80,) 247 Solar ultraviolet radiation also partially destroys 15 by NO,5NO+0 — 1.<4000A (V1-104) ‘The ratio ofthe rate of ozone destruction with and without NO,(NO + NO} the catalytic ratio p, is (208, 537, 538) (VE-105) Since ky ¥ 10,000 x kyoo at 230K, an approximate temperature in the stratosphere, even a very small fraction of NO,, 001% of O5, present in the stratosphere is as effective as destroying ozone by (VI-100), Besides the NO-NO, cycle, another effective catalytic cycle is a CI-CIO chain [Molina and Rowland, (711) Crutzen (252)). The Cl atoms are produced from the photolysis of chlorofluoromethanes, used as refrigerants and as aerosol propellants. CFC SCFCL4Cl 1.<2300A (1-106) The Clatoms produced react with ozone Cl+0,+Cl0 +0; (vi-107) followed by Cl0+0+C1+0, net 0 +0420; Further discussion of the CI-CIO chain is given in Section VIII-2, (V-108) Vi-12, SULFUR DIOXIDE (SO,) ‘The ground state SO, is TA, with an O—S —O angle of 119.5°. The bond energy Do(OS—O) is $.65 + 0.01 eV (767). Sulfur dioxide exhibits complex absorption spectra in the near ultraviolet as well as in the vacuum ultraviolet regions, There are three main regions of absorption in the ultraviok aan extremely weak absorption in the 3400 to 3900 A, a weak absorption in the 2600 to 3400 A, and a strong absorption in the 1800 to 2350 A region, Figures VI- Sa through VI- ISe show the absorption coefficients of SO, in the near ultraviolet as well as in the vacuum ultraviolet regions. The dissociation of SO; to SO + O starts below about 2190 A. Above this wavelength SO, exhibits strong fluorescence and phosphorescence. In spite of many studies the complete analysis of the ultraviolet absorption spectrum has not been successful [Herzberg (16), p. S11]. The spectroscopy and photochemistry of SO, may be conveniently discussed for fourPhotochemistry of Tr sions of absorption: 3400 to 3900 A region 2600 to 3400 A region 1800 to 2400 A region 1050 t0 1800 A region 1.12.1. Spectroscopy and Photochemistry of SO, in the 3400 to 3900 A Region sorption is extremely weak in this region (see Fig. VI-1Su). A rotational valyss indicates that the upper state is 3°B, [Brand ct al. (128)] with an eelronic origin at 3.194 eV. An additional state *A, near 3700 A may be «sent in this region (135). The triplet emission lifetime of about 1 msec has vent measured by Collier et al. (228) and by Sidebottom et al, (876) when 5 was excited by the 3828.8 A laser line. This lifetime is much shorter sn, 7 msee measured by Caton and Duncan (197). A collision-fee lifetime 2.7 msec has been obtained by Briggs et al. (149). The lifetime of a few iliseconds is much shorter than that expected from the integrated absorp: vn coelficient (1.7 x 10"? sec), indicating that the radiationless transition soo seo ' doo R @ 4, VI-IS. (a) Absorption coefficients of SO,. 3400 (0 4000 A rej 1°" em~', base 10, room temperature. Reprinted with permi tom, C. C. Badcock, G. E. Jackson, J. G. Calvert, G. W. Reinhardt, and E. K. Environ. Sci. Technol. 6, 72 (1972). Copyright by the American Chemical ‘riety. (6) Absorption coefficients of SO,. 1900 t0 2150 A revi Golomb et al 197), 2100 to 3100 A region, From Warneck etal. (10088); ks its of aim" 1, bave e, 0°C. Reprinted by permission. Copyright 1964 by the American In Physics. (€) Absorption coefficients of SO, in the te units of atm”* em” *, base ¢, 0°C. From Galomb etal. (407), reprinted by permission, vpyright 1962 by the American Institute of Physics. yy doo elo . . WM i = VAIS. (cont) ayWoo) Woo woo woo, A o Fig. VIALS. (cont) 250 1e(SO}) 281 to the ground state is a predominant process. ssscuet yield of phos Dhorescence is estimated to be 0.12 + 009 in comparison with the phosphorescence quantum yield of biacetyl-cyclohexane mixtures [Sidebottom et al. (876)). On the other hand, Strickler et al. (941) have obtained « quatntum yield of0.07 from the measured phosphorescence decay rate at zero pressure, 1.12 4020 x 10° sce”, and the calculated radiative rate constant (79 + 5 see" #), Nelson and Borkman (732)have measured the lifetime and quantum yield of solid SO; at low temperatures. They have found $'%0,0°B,) has a somewhat longer lifetime than $'°0 0) Very recently Su et al (953a) obtained a collision-free lifetime of SO,(°B,) 018.1 + 2.5 msec, which is considerably longer than that reported previously ‘The new lifetime is in reasonable agreement with that calculated from the integrated absorption coefficient using (1-910), indicating that the phospho: Fescence quantum yield is near unity. Apparently, intersystem crossing to the ground state is not important as was predicated by Bixon and Jortner (on a theoretical basis (110) The self-quenching rate constant (876) is 6.64 x 10°" cm? molec” see”. The quenching products may be SO; or SO + SO, $0,(°B,) + SO; + 280, (vE-109) $030°B,) + SO, + SO + SO, (VETO) ‘The quenching rates of the triplet by CO, Nz, Os, HO, Ar, He, Xe, CO; 4, NO, and hydrocarbons have been measured by Calvert et al, (53, 517. 824, 877, 879, 1005), The quenching rate by NO is almost gas kinetic, white that by O, is unexpectedly small (JO ' em? molec”! sec~') (824, 879), The quenching by CO produces substantial amounts of CO, at higher temperatures, while at room temperature only 8°, of the bimolecular collision results in CO, (517). The rate constants for Nz, CO, CO, CH, and the rare gases are all very similar (10” " em? molec”! sec”') VI-12.2. Spectroscopy and Photochemistry in the 2600 10 3400 A Region The rotational steucture in this region is very complex and no conclusive analysis has been made. The *B, state is tentatively assigned by Herzberg {(16), p. 605], Another state, "4p, has been suggested (472) near the 'B, state, Brand and Nanes (130) have recently assigned 'B, for the 3000 to 3400 A region. At shorter wavelengths may lie the '4,~'A, transition (130) On the other hand, Hamada and Merer, (434, 435) and Dixon and Halte (288) have concluded that the upper state is "Ay and the forbidden transition "Ay", becomes allowed by the excitation of the v antisymmetric stretching282. Photochemistry of Triatomic Molecules vibration of hy symmetry. The origin of the B('8,) X("4,) transition lies in the region 3100 to 3160 A (435). According to a recent study by Brand et al. (135). quasicontinuous absorption underlying the structured A',-K'A, bands is he B'B,-R', transition and the "By state is strongly coupled ‘with the X', state. The "4, state is vibrationally coupled with 'B, to have the necessary oscillator strength in the 'A,~'A, transition. Greenough and Duncan (421) have obtained a fluorescence lifetime of 42 yosce when SO, is excited by light of wavelengths neur 3000 A. Sidebottom et al, (878) have obtained a zero pressure lifetime of 36 jsee at the 2662 A excitation, but it appears to decrease with less excess vibrational energy. On the other hand, Brus and McDonald indicate 156, 157) that at least two states appear (0 be involved in fluorescence by light absorption in the 2600 to 3200 A region, one with a short collision-free lifetime (x4 = 50 psec) and the other with a long collision-free lifetime (r,, = 80-530 j:sec). Further- more, t,, is longer at the longer exciting wavelength, while ty appears to be independent of the exciting wavelength, The state with the short lifetime is quenched very rapidly (>10 x 107! cm molec”! see”"), while the state With the long lifetime is quenched with unit collision efficiency. The measured fetime s, is much longer than that ealculated from the integrated absorp tion coefficient (0.2 psec) (421). This anomalous lifetime, according. to Douglas (324) (see Section H-2.1), can be expluined on the basis of the imteraction of the singlet state with a low-lying metastable state or the ground state. As a result ofthis interaction the singlet state is “diluted” by the state that does not combine with the ground state. Therefore, the lifetime ismuch longer than that calculated from the integrated absorption coefficient The lengthening of the lifetime, as well as the eflicent quenching of the singlet state, is explained by the interaction of the vibrational levels of the singlet state with those of the ground state (386). The Mluorescence quantum Yield appears to be near unity (156, 183). Brand et al. (135) suggest that the two lifetimes x, and x, are, respectively, from the AA, and BB, states ‘At low pressures of SO, broad structureless emission with a maximum at about 3600 A was excited by light of wavelengths near 3000 A [Strickler and Howell (940), Mettee (698)]. This emission is due to fluorescence from the lowest singlet state, At higher pressures some new relatively sharp vibrational structure starts to appear in the region 3900 to 4900 A. The bands can be ascribed to the transition from a vibrationally equilibrated Uriplet state to the ground in comparison with the absorption spectrum (698, 940). Phosphorescence is seen by the 3130 A excitation even at the lowest possible pressure [Caton and Gangadharan (198)} ‘The following reaction mechanism may be presented for photochemical reactions in this VI-I2. Sulfur Dioxide (SO) 283 region so, "'s0, (ii ‘SO, + SO, +280, (VI-112) 'S0 + 80; + 'S0, + SO; (VEU) ‘SO, + SO, + hv (VE-114) 'SO, +SO, Kus (VE-IIS) 'SO, +*SO, kare (VI-116) §§0, +80; +h kya (view?) ‘SO, +SO, Kus (VI-118) 4§0; + SO; +280; hu (VE-119) ‘SO, + SO, +SO, + SO Kio (V1-120) The 'SO, und *SO, represent the first singlet and triplet states, respectively The reaction 'SO, + SO, produces °SO, with about 8", efficiency [Rao etal. (8239) The photolysis of pure SO; in the region 2500 to 3200 A has produced SOs (@so,, = 0.08) (775, 785) and SO (69, 523). Otsuka and Calvert (745) conclude that SO, is produced from (VI-120) and ky 9 > kyo, while James ct al, (523) believe that *SO, is not 3°B, but a nonphosphorescent *A,. The triplet SO, decays only 10%, by emission, that is, 10k,, described earlier in Section VI- 12.1, (According to very recent results by Su et al. (95%), Ary = 1.2 % 10 sec~', kyyy * 0.) The main unimolecular reaction of 'SO; appears to be Muorescence (156, 183, 482) that is, kis, Kip = 0. The quenching of 'SO, and 'SO, by foreign gases has been extensively studied by Calvert and Heicklen and their coworkers. Quenching gases include biacetyl (345, 482, 823), CO, (824), N, (483), CO (200, 201, 1003), C.F 4s (200), hydrocarbons (53, 651), and other simple guses (785, 936, 1004). To explain the pressure dependence on the yield of the sensitized biacety! emission (345, 484) and on CO oxidation (200, 201, 1003), it appears necessary to assume that singlet and triplet states other than 'B, and °B, arc involved The singlet excited state of SO seems important only as a source of "SO ‘molecules through collision-induced intersystem crossing. The ?SO, formed subsequently participates in chemical reactions with CO, SO}, CaF y, and oletins (272), The reaction of SO; with C.F, produces CF,O as a product (05 of the total quenching) (200, 877). The reaction of SO, with olefins produces sullinie acids with collision efficiencies ranging from 0.14 to 0S (877), The reaction products may be formed from a common intermediate iplet diradical ofa SO, RH complex. The reactions of *SO, with 2-butenes = Fave as

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