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CHIROPTICAL
SPECTROSCOPY
CHIROPTICAL
SPECTROSCOPY
Fundamentals and
Applications
Prasad L. Polavarapu
Vanderbuilt University, Nashville, Tennessee, USA
Boca Raton London New York
CRC Press is an imprint of the

Taylor & Francis Group, an informa business
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Version Date: 20160711
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Library of Congress Cataloging‑in‑Publication Data
Names: Polavarapu, Prasad L.

Title: Chiroptical spectroscopy : fundamentals and applications / Prasad L. Polavarapu.
Description: Boca Raton : Taylor & Francis, 2017. | “A CRC title.” | Includes
bibliographical references and index.
Identifiers: LCCN 2016009687 | ISBN 9781420092462 (alk. paper)
Subjects: LCSH: Optical spectroscopy. | Spectrum analysis. | Vibrational spectra.
Classification: LCC QC454.O66 P65 2017 | DDC 543/.5--dc23
LC record available at https://lccn.loc.gov/2016009687
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To Bharathi, Sruthi, and Aaseesh
Contents
Preface .....................................................................................................................xv
Author .................................................................................................................. xvii
1. Polarized Light ................................................................................................1

1.1 Introduction to Light ............................................................................1
1.2 Polarization States .................................................................................4
1.2.1 Dependence on Phase Difference ..........................................5
1.2.2 Dependence on Amplitude Difference ............................... 11
1.2.3 Dependence on Both Phase and Amplitude Differences ....12
1.2.4 Generalization ........................................................................ 14
1.2.5 Advanced Representations ................................................... 14
1.3 Energies ................................................................................................ 14
References ....................................................................................................... 15
2. Chiral Molecules........................................................................................... 17
2.1 Classification of Molecules ................................................................ 17
2.2 Configurations of Chiral Molecules ................................................. 21
2.2.1 Central Chirality ....................................................................22
2.2.2 Axial Chirality........................................................................ 27
2.2.3 Helical Chirality ..................................................................... 29
2.2.4 Planar Chirality......................................................................30
2.2.5 Propeller Chirality ................................................................. 31
2.2.6 Other Sources of Chirality.................................................... 31
2.3 Conformations ..................................................................................... 32
2.4 Biomolecular Structures..................................................................... 35
References ....................................................................................................... 35
3. Interaction of Circularly Polarized Light with Chiral Molecules ...... 37

3.1 Introduction ......................................................................................... 37
3.2 Optical Rotation .................................................................................. 37
3.3 Circular Dichroism .............................................................................42
3.4 Vibrational Raman Optical Activity (VROA) ................................. 46
3.5 Summary ..............................................................................................54
References ....................................................................................................... 55
4. Quantum Chemical Formulation of Chiroptical Spectroscopy..........57

4.1 Interaction of Molecules with Electric Field.................................... 58
4.2 Time-Independent Perturbation Theory ......................................... 60
4.2.1 First-Order Corrections ......................................................... 61
4.2.2 Molecules in Static Electric Field ......................................... 62
4.2.3 Second-Order Corrections ....................................................64
vii
viii Contents
4.3 Time-Dependent Perturbation Theory ............................................ 66

4.4 Molecules in Dynamic Fields ............................................................ 67
4.4.1 Electric Field Perturbation .................................................... 68
4.4.1.1 Dynamic Electric Dipole–Electric Dipole
Polarizability ........................................................... 68
4.4.2 Magnetic Field Perturbation................................................. 71
4.4.2.1 Dynamic Electric Dipole–Magnetic Dipole
Polarizability ........................................................... 71
4.5 Interaction of Molecules with CPL ................................................... 72
4.5.1 Electric and Magnetic Fields of CPL ................................... 73
4.5.1.1 Electric Field ............................................................ 73
4.5.1.2 Magnetic Field ........................................................ 73
4.5.2 Electric Dipole Moment Induced by Electric and
Magnetic Fields of CPL ......................................................... 74
4.5.3 Specific Optical Rotation....................................................... 78
4.5.4 Transition Rates for Molecules Interacting with CPL ...... 79
4.5.5 Relation to Experimental Absorption and Circular
Dichroism................................................................................84
4.6 Transition Polarizabilities .................................................................. 87
4.7 Summary .............................................................................................. 87
References ....................................................................................................... 88
5. Prediction of Chiroptical Spectra..............................................................89

5.1 Introduction ......................................................................................... 89
5.2 Spectral Predictions Using Quantum Chemical Methods ........... 89
5.2.1 Optical Rotatory Dispersion.................................................90
5.2.1.1 Practical Considerations ........................................ 93
5.2.2 Electronic Absorption and Circular Dichroism Spectra ....94
5.2.2.1 Practical Considerations ........................................ 95
5.2.3 Vibrational Absorption and Circular Dichroism Spectra ... 95
5.2.3.1 Practical Considerations ...................................... 101
5.2.4 Vibrational Raman and Raman Optical Activity
spectra.................................................................................... 102
5.2.4.1 Practical Considerations ...................................... 104
5.2.4.2 Resonance ROA Spectra ...................................... 105
5.2.4.3 Surface-Enhanced VROA Spectra ...................... 105
5.2.5 Role of Solvation on Chiroptical Spectra .......................... 105
5.2.6 Approximate Methods for Large Molecules:
Cartesian Tensor Transfer and Fragmentation ................ 108
5.2.7 Accurate Calculations on Large Molecules:
Molecules-in-Molecules Fragmentation Method ............ 109
5.3 Spectral Predictions Using Approximate Models ........................ 110
5.3.1 Optical Rotatory Dispersion............................................... 110
5.3.2 Electronic Circular Dichroism ........................................... 110
Contents ix
5.3.3 Vibrational Circular Dichroism ......................................... 111

5.3.4 Vibrational Raman Optical Activity ................................. 112
5.4 Summary ............................................................................................ 112
References ..................................................................................................... 113
6. Conformational Analysis..........................................................................123
6.1 Conformational Analysis of Solute Molecule ................................... 123
6.1.1 Designation of Bonds.............................................................. 124
6.1.2 Ring-Puckering Angles .......................................................... 124
6.1.3 Symmetries of Generated Conformations ........................... 126
6.1.4 Structures with Equivalent Energies .................................... 126
6.1.5 Atropisomers ........................................................................... 127
6.1.6 Molecular Ions and Radicals ................................................. 128
6.1.7 Dimeric Structures .................................................................. 128
6.1.8 Enantiomer Structures ............................................................ 129
6.1.9 Boltzmann Populations .......................................................... 129
6.2 Conformational Analysis of Solute–Solvent Clusters...................... 130
6.3 Summary ................................................................................................ 130
References ..................................................................................................... 130
7. Experimental Methods for Measuring Chiroptical Spectra ..............133
7.1 Introduction ....................................................................................... 133
7.2 Optical Rotatory Dispersion ............................................................ 133
7.2.1 Optical Rotation of Liquid Solutions ................................ 133
7.2.2 OR of Gas-Phase Samples ................................................... 140
7.2.3 Time-Resolved ORD Measurements ................................. 141
7.2.4 Evanescent Wave OR Measurements ................................ 141
7.3 Circular Dichroism Measurements ................................................ 141
7.3.1 Dispersive Spectrometers ................................................... 144
7.3.2 FT Spectrometers ................................................................. 145
7.3.3 Potential Artifacts ................................................................ 147
7.3.4 Practical Considerations ..................................................... 150
7.3.5 Tunable Laser-Based Spectrometers ................................. 157
7.3.6 Time-Resolved Circular Dichroism .................................. 157
7.3.7 Nonlinear Spectroscopic Methods .................................... 158
7.4 Interconversion of CD and ORD ..................................................... 158
7.5 VROA Measurements ....................................................................... 159
7.5.1 Normal VROA Measurements ........................................... 159
7.5.2 FT-VROA Measurements .................................................... 163
7.5.3 Resonance VROA Measurements ...................................... 163
7.5.4 Induced Resonance ROA Measurements ......................... 164
7.5.5 Surface-Enhanced VROA Measurements ........................ 164
7.5.6 Coherent Anti-Stokes VROA Measurements ................... 164
7.5.7 Magnetic VROA Measurements ........................................ 164
7.6 Related Methods ............................................................................... 165
x Contents
7.7 Summary ............................................................................................ 165

References ..................................................................................................... 165
8. Comparison of Experimental and Calculated Spectra ....................... 175

8.1 Comparison of Experimental and Calculated Spectra ................ 175
8.1.1 Qualitative Comparisons .................................................... 176
8.1.2 Quantitative Comparisons ................................................. 178
8.1.3 Numerical Measures of Similarity .................................... 180
8.1.3.1 Carbó-Similarity Index (SI) ................................. 180
8.1.3.2 Neighborhood Similarity .................................... 181
8.1.3.3 Enantiomeric Similarity Index (ESI).................. 182
8.1.3.4 Spectral Similarity (Sim) ...................................... 183
8.1.3.5 Square Root of the Squared Difference............. 183
8.2 Comparison of Experimental and Calculated Ratio Spectra...... 184
8.3 Significance of Similarity Measure Values .................................... 192
8.4 Summary ............................................................................................ 193
References ..................................................................................................... 194
9. Chiral Aggregation, Equilibria, and the Horeau Effect .....................197

9.1 Homochiral Monomer–Dimer Equilibrium.................................. 198
9.1.1 Analysis of SOR Data .......................................................... 201
9.1.2 Analysis of Absorption Spectral Data .............................. 204
9.1.3 Analysis of CD Spectral Data ............................................. 207
9.1.4 Analysis of Vibrational Raman and VROA Spectral
Data ........................................................................................ 207
9.2 Heterochiral Monomer–Dimer Equilibrium................................. 208
9.2.1 Equilibria with K ht = 2K ...................................................... 209
9.2.1.1 Analysis of SOR Data........................................... 210
9.2.1.2 Analysis of Absorption Spectral Data ............... 213
9.2.1.3 Analysis of CD Spectral Data ............................. 213
9.2.1.4 Analysis of Vibrational Raman and VROA
Spectral Data ......................................................... 214
9.2.2 Equilibria with K ht Not Equal to 2K .................................. 214
9.2.2.1 Analysis of SOR Data........................................... 214
9.2.2.2 Analysis of Absorption/Raman Spectral
Data for Racemic Mixtures ................................. 216
9.3 Equilibrium between Secondary Structures of Biological
Systems ............................................................................................... 217
9.4 Summary ............................................................................................ 218
References ..................................................................................................... 219
10. Applications of Chiroptical Spectra .......................................................221

10.1 Introduction ....................................................................................... 221
10.2 Spectra–Structure Correlations.......................................................223
10.2.1 ORD Spectra .........................................................................223
10.2.2 ECD Spectra .......................................................................... 229
Contents xi
10.2.3 VCD Spectra.......................................................................... 230

10.2.4 VROA Spectra ....................................................................... 231
10.3 Spectral Predictions Using Approximate Models ........................ 232
10.3.1 ORD Spectra ......................................................................... 232
10.3.2 ECD Spectra .......................................................................... 232
10.3.3 VCD Spectra..........................................................................234
10.3.4 VROA Spectra ....................................................................... 235
10.4 Spectral Predictions Using Quantum Chemical
Calculations ....................................................................................... 235
10.4.1 Determination of the Molecular Structures..................... 235
10.4.1.1 Fluorinated Ethers .............................................. 236
10.4.1.2 Halomethanes ..................................................... 237
10.4.1.3 Molecules with Chirality Imparted by
Isotopic Substitution .......................................... 238
10.4.1.4 Metal Wires ......................................................... 239
10.4.1.5 Fullerenes ............................................................ 240
10.4.1.6 Helicenes.............................................................. 241
10.4.1.7 Metal Nanoparticles........................................... 243
10.4.1.8 Organic Nanoparticles ...................................... 244
10.4.1.9 Cryptophanes ..................................................... 244
10.4.1.10 Cyclophanes ........................................................ 245
10.4.1.11 Atropisomers ...................................................... 247
10.4.1.12 Supramolecular Aggregates ............................. 250
10.4.1.13 Pharmaceutical and Antimicrobial
Compounds ......................................................... 256
10.4.1.14 Transport Antibiotics ......................................... 260
10.4.1.15 Pesticides and Herbicides.................................. 262
10.4.1.16 Thiophenes .......................................................... 262
10.4.1.17 Chiral Sulphur Compounds ............................. 263
10.4.1.18 Chiral Phosphorous Compounds .................... 265
10.4.1.19 Chiral Selenium Compounds ........................... 267
10.4.1.20 Chiral Pheromones ............................................ 267
10.4.1.21 Fungal/Plant Metabolites ................................. 268
10.4.1.22 Carbohydrates ..................................................... 269
10.4.1.23 Transition Metal Complexes ............................. 270
10.4.1.24 Natural Products ................................................ 270
10.4.1.25 Polymers .............................................................. 271
10.4.1.26 Biomolecular Structures .................................... 275
10.4.1.27 Other Molecules ................................................. 277
10.4.1.28 Role of Intramolecular CT ................................. 277
10.4.2 Correcting the Incorrect or Ambiguous ACs................... 278
10.4.2.1 Troger’s Base ......................................................... 278
10.4.2.2 1,1-Dimethyl-2-Phenylethyl Phenyl
Sulfoxide (DPPS)................................................... 278
10.4.2.3 2-(1-Hydroxyethyl)-Chromen-4-One (HECO) ....279
xii Contents
10.4.2.4 3,3′-Diphenyl-[2,2′-Binaphthalene]-1,1′-Diol
(Vanol) .................................................................... 279
10.4.2.5 Chromanes ............................................................ 280
10.4.2.6 Remisporine B....................................................... 280
10.4.2.7 Natural Products .................................................. 281
10.5 Analytical Applications ................................................................... 281
10.6 Chiroptical Spectroscopy in Undergraduate Teaching
Laboratories ....................................................................................... 282
10.6.1 Inversion of Sucrose............................................................. 282
10.6.2 Monomer–Dimer Equilibrium ...........................................284
10.6.3 Other Experiments ..............................................................284
10.7 Summary ............................................................................................284
References ..................................................................................................... 285
Appendixes
A1. Polarization States and Stokes Parameters ........................................... 317

A1.1 Real-Form Expressions for Polarization States ............................. 317
A1.2 Complex-Form Expressions for Polarization States ..................... 318
A1.3 Stokes Parameters ............................................................................. 318
References ..................................................................................................... 321
A2. Kramers–Kronig Transformation ...........................................................323

A2.1 KK Transformation of Molar Ellipticity into Molar Rotation ..... 323
A2.2 Numerical Integration Methods for KK Transform ..................... 324
References ..................................................................................................... 325
A3. Spectral Simulations .................................................................................. 327

A3.1 Gaussian Distribution ...................................................................... 328
A3.2 Lorentzian Distribution ................................................................... 330
A3.3 Absorption Spectral Simulations .................................................... 331
A3.3.1 Vibrational Absorption Spectral Simulation as a
Function of Wavenumber ................................................... 331
A3.3.2 Electronic Absorption Spectral Simulation as a
Function of Wavelength ...................................................... 332
A3.4 Circular Dichroism Spectral Simulations......................................334
A3.4.1 VCD Spectral Simulation as a Function of
Wavenumber.........................................................................334
A3.4.2 ECD Spectral Simulation as a Function of
Wavelength ........................................................................... 335
A3.5 Vibrational Raman and Raman Optical Activity Spectral
Simulations ........................................................................................ 336
A3.6 Spectral Simulation Software .......................................................... 338
References ..................................................................................................... 338
Contents xiii
A4. Exciton Coupling, Exciton Chirality, or Coupled Oscillator Model .... 339
A4.1 Two Noninteracting Groups ............................................................340
A4.2 Two Degenerate Interacting Groups ..............................................342
A4.2.1 Two Degenerate Interacting Groups without
Intrinsic Magnetic Dipole Transition Moments ..............348
A4.2.2 Two Degenerate Interacting Groups with Intrinsic
Magnetic Dipole Transition Moments .............................. 355
A4.3 Two Nondegenerate Interacting Groups ....................................... 355
A4.4 Multiple Interacting Transitions ..................................................... 360
References ..................................................................................................... 361
A5. Averaging Properties Using Boltzmann Populations .........................363

A5.1 Conformational Averaging .............................................................. 363
A5.2 Vibrational Averaging ......................................................................364
Reference .......................................................................................................365
A6. Monochromators and Interferometers ...................................................367

A6.1 Monochromators ............................................................................... 367
A6.2 Interferometers .................................................................................. 368
A6.2.1 Amplitude Division Interferometers ................................ 369
A6.2.2 Polarization Division Interferometers .............................. 370
References ..................................................................................................... 372
A7. Polarization Modulation ...........................................................................373

A7.1 Signal Processing in Dispersive CD Spectrometers..................... 374
A7.2 Calibration of Dispersive CD Spectrometers ................................ 377
A7.3 Signal Processing in FTCD Spectrometers .................................... 380
A7.4 Polarization Scrambling ................................................................... 383
References .....................................................................................................384
A8. Units and Conversions ..............................................................................385

A8.1 Constants .......................................................................................... 385
A8.2 Different Units of Energy............................................................... 385
A8.3 Unit Conversions ............................................................................. 385
A8.4 Hartree.............................................................................................. 386
A8.5 Bohr Radius, a0................................................................................. 386
A8.6 Conversion between Dimensionless Normal Coordinate qk
to Normal Coordinate Qk ............................................................... 386
A8.7 Conversion of Dipole Strength to Absorption Intensity in
km⋅mol-1 ............................................................................................ 387
A8.8 Conversion between Absorption Intensity and Electric
Dipole Moment Derivatives........................................................... 387
A8.9 Conversion between Dipole Strength Di and Oscillator
Strength fi ......................................................................................... 388
xiv Contents
A8.10 Conversion of Dipole Strength to Absorption Intensity in

cm3⋅mol–1 ........................................................................................... 388
A8.11 Conversion of Experimental Integrated Absorption
Intensities to Dipole Strengths ...................................................... 389
A8.12 Conversion of Experimental Integrated Circular Dichroism
Intensities to Rotational Strengths ............................................... 389
A8.13 Units for Raman and Raman Circular Intensity Difference
Activities........................................................................................... 390
A9. References for Chiroptical Spectroscopic Studies on Transition
Metal Complexes ........................................................................................393
Index .....................................................................................................................407
Preface
Optical activity is a phenomenon that is well known to scientists (chemists,

biochemists, and physicists, in particular). For some, the familiarity with
optical activity comes from the rotation of plane polarized visible light, often
referred to as optical rotation (OR). This property when normalized for con-
centration and path length is called specific rotation (SR), and when displayed
as a wavelength resolved plot is called optical rotatory dispersion (ORD). In
recent years, SR is often referred to as specific optical rotation (SOR). Another
familiar form of optical activity is the differential absorption of left and right
circularly polarized visible light, often referred to as circular dichroism (CD)
and more specifically as electronic circular dichroism (ECD). The scientific
research in ORD and ECD originated in the nineteenth century and has been
widespread. For aged research areas such as these, one may wonder if there
is anything new that is left to be discovered. It would not be surprising for
people with an open mind that such complacency can be out of place in sci-
entific research. Not only did significant new developments take place in
these areas but also new variants of optical activity were discovered in the
late twentieth century. The new variants include CD in the infrared region,
known as infrared vibrational circular dichroism (VCD), and differential
vibrational Raman scattering of left and right circularly polarized visible
light, known as vibrational Raman optical activity (VROA). These two new
areas are referred together as vibrational optical activity (VOA). New devel-
opments in the methods for measurement and interpretation of OR and ECD
have also taken place at about the same time. The four methods mentioned
above (ORD, ECD, VCD, and VROA) represent four different branches of chi-
roptical spectroscopy. An increasing number of research groups have started
utilizing these methods in the quest for advancing science. Since most of
the research in individual research laboratories is carried out by graduate
and undergraduate students, an influx of new young scientists has occurred.
The excellent books (Barron 2004; Charney 1985; Nafie 2011; Polavarapu 1998;
Stephens et al. 2012) available in the market on this subject have focused
either on one or two of these areas or are written for people with an advanced
background. As a result, a starting young scientist is often burdened with
collecting pieces of information from different sources. My desire for writing
a book that explains chiroptical spectroscopy starting from an elementary
level, and progressing to the level of helping to adopt this research area, has
emerged in this context with beginning researchers in mind.
My goal for this book is to provide a convenient and comfortable refer-
ence for those who are novice to chiroptical spectroscopy. At the same time,
I wanted to lead them to a level where they can feel comfortable to pursue the
advanced level of inquiry, if they so desire. At the first instinct, it may sound
xv
xvi Preface
impossible to achieve these goals in one monograph. Nevertheless, I tried to

achieve these goals by providing the main text at an elementary level, keep-
ing novice students in mind, in an easily readable language. However, when
it comes to describing the quantum mechanical underpinnings, there is no
escape from jumping into involved mathematical formulations. To make this a
smooth transition, I have presented the equations in as much detail as possible,
so a starting researcher does not have to get bogged down in deriving them.
It is my hope that this book will serve as a guiding source for both entry
level and seasoned practitioners of these research areas, as much of the
needed information for both groups of researchers has been provided. In
addition, this book is intended to serve as a textbook for an introductory
course on chiroptical spectroscopy.
Greater benefit to society can be realized if an author can help the novice
understand the material easily and thoroughly. Therefore, it is my sincere
hope that this book will attract and help a new generation of researchers in
chiroptical spectroscopy to become proficient in this scientific area.
Finally, I am privileged to be associated with excellent teachers, research
advisers, collaborators, postdoctoral research associates, graduate students,
and undergraduate students, who conducted research with me in the last
four decades. With immense pleasure, I acknowledge my productive asso-
ciation with them and express my gratitude for facilitating the never-ending
learning process.
Prasad L. Polavarapu
Vanderbilt University
References
Barron, L. D. 2004. Molecular Light Scattering and Optical Activity, 2nd ed. Cambridge,
UK: Cambridge University Press.
Charney, E. 1985. The Molecular Basis of Optical Activity. Malabar, FL: Krieger
Publishing Co.
Nafie, L. A. 2011. Vibrational Optical Activity: Principles and Applications. New York,
NY: John Wiley and Sons.
Polavarapu, P. L. 1998. Vibrational Spectra: Principles and Applications with Emphasis on
Optical Activity. New York, NY: Elsevier.
Stephens, P. J., F. Devlin, and J. R. Cheeseman. 2012. VCD Spectroscopy for Organic
Chemists. London, UK: CRC Press.
Author
Prasad L. Polavarapu, PhD, was born and raised in Gudlavalleru, a small

village in the state of Andhra Pradesh, India. His parents were farmers by
profession and did not have a formal educational background. Nevertheless,
his father provided never-ending support for him to pursue higher education.
Dr. Polavarapu joined the PhD program at the Indian Institute of
Technology, Madras (now renamed as Chennai), after earning his master’s
degree from Birla Institute of Technology, Pilani. He earned his doctoral
degree under the supervision of the late Professor Surjit Singh at the Indian
Institute of Technology, where his research focused on the interpretation
of vibrational infrared absorption intensities. On completion of his doc-
toral degree, he moved to the laboratory of Professor Duane F. Burrow at
the University of Toledo, Toledo, Ohio, in 1977 for postdoctoral research
on vibrational Raman optical activity. In the subsequent year, he joined
the laboratory of Professor Laurence A. Nafie at Syracuse University,
Syracuse, New York, where he carried out research work on vibrational
Raman optical activity and vibrational circular dichroism. Dr. Polavarapu
joined Vanderbilt University, Nashville, Tennessee, in 1980 as an assistant
professor of chemistry. He was promoted to associate professor in 1987
and then to professor in 1994.
Dr. Polavarapu has made pioneering contributions in the research areas
of optical rotation, vibrational Raman optical activity, vibrational circular
dichroism, and electronic circular dichroism. He has published approxi-
mately 260 peer-reviewed research papers in leading scientific journals.
Dr. Polavarapu edited the book Polarization Division Interferometry, which
was published in 1997 by John Wiley & Sons. One of the contributors of that
book, Dr. John Mather, won the 2006 Nobel Prize in Physics. Dr. Polavarapu
wrote the book Vibrational Spectroscopy: Principles and Applications with
Emphasis on Optical Activity, which was published by Elsevier in 1998. More
recently, he coedited two volumes on Comprehensive Chiroptical Spectroscopy,
which were published by John Wiley & Sons in 2012.
Dr. Polavarapu was awarded the Jeffrey Nordhaus Award in 2010 for excel-
lence in undergraduate teaching at Vanderbilt University. He was elected as
a fellow of the American Association for Advancement of Science in 2012
for distinguished contributions to the field of chiral molecular structure
determination.
Dr. Polavarapu continues his research work in chiroptical spectroscopy
while teaching undergraduate and graduate courses at Vanderbilt University.
xvii
1
Polarized Light
Interaction between electromagnetic radiation and matter is the basis of a

broad research area that is generally categorized as spectroscopy. When the
matter under consideration is made up of chiral molecules (see Chapter 2), a
special branch of spectroscopy, labeled as chiroptical spectroscopy, becomes
pertinent. The words “chiroptical spectroscopy” can be construed to mean
the study of chiral systems using optical spectroscopy methods. To under-
stand the principles of chiroptical spectroscopy, it is necessary to gain insight
into the properties of electromagnetic radiation, chiral molecules, and the
interaction between them. These concepts form the basis for the starting
chapters in this book.
1.1 Introduction to Light

Visible light represents electromagnetic radiation that can be detected with
the human eye. This statement automatically raises thoughts about “invis-
ible” light. To distinguish between visible and invisible light, we need to con-
sider the wave properties of electromagnetic radiation. A wave (see Figure
1.1a) is associated with periodic oscillatory variation of its height (referred
to as amplitude) in time. Two identical points in a wave constitute one cycle.
For example, two consecutive crest points, two consecutive trough points, or
three consecutive zero points constitute one cycle or one wave. If an observer
stands at one point and watches the waves pass by in time, the number of
cycles passed in a given second is labeled as frequency (ν). The unit of fre-
quency is cycles/second (or simply s−1), which is designated as hertz (Hz;
1 Hz = s−1). A cosine wave with unit amplitude is represented by the func-
tion cos2π ν t, where t stands for time in seconds. This cosine wave is shown
in Figure 1.1a, where the definition of a cycle is depicted. The alternate rep-
resentations of frequency of oscillation are wavelength and wavenumber. If
a stationary wave is held along the z axis (see Figure 1.1b) and the distance
between three consecutive zero points (or between two crests or between
two troughs) of that wave is measured, then that distance is labeled as wave-
length and represented by symbol λ [expressed as meters/cycle or simply as
meters (m)]. This definition of wavelength is shown in Figure 1.1b, where a
1
2 Chiroptical Spectroscopy: Fundamentals and Applications
Amplitude
0
Time, t
One cycle
–1
(a)
1
Amplitude
0
z axis
λ
–1
(b)
FIGURE 1.1
(a) Depiction of the amplitude and cycle of an oscillating cosine wave, cos 2π νt, with unit
amplitude as a function of time. (b) Depiction of the amplitude and wavelength λ of an oscil-
lating cosine wave, cos (2π z/λ), propagating along the z axis with unit amplitude.
wave with unit amplitude, represented by the cosine function cos2π z/λ, is
depicted. The product of wavelength and frequency of a wave is equal to the
speed of that wave c, which is expressed as m⋅s−1:
m cycle m
c = λν = × = = m s−1 (1.1)
cycle s s
If an electromagnetic wave passes through a medium with refractive index
nm, then the speed of electromagnetic wave changes as cm = c/nm. Then,
Equation 1.1 modifies as cm = λm ν, where λm is the wavelength of the wave
in that medium (Levine 2009). For the current purposes, consider the waves
propagating in vacuum, where nm = 1. Just as the number of cycles per sec-
ond is labeled as frequency, the number of waves per unit length is labeled
as wavenumber (ν). Since one wave occupies a length of λ, wavenumber is
Polarized Light 3
equal to the reciprocal of wavelength. Therefore, ν = 1/λ, and its units are
expressed in m−1. Thus, an alternate form of Equation 1.1 is as follows:
m
ν = νc = m−1 × = s−1 (1.2)
s
The wavelength λ (or equivalently frequency ν or wavenumber ν) of a wave
determines the properties of that wave. Human eyes respond to the electromag-
netic waves of wavelength between ~400 and 800 nm (1 nm = 10−9 m), and this
portion of electromagnetic radiation is referred to as the visible light. The dif-
ferent colors that human eyes can recognize (violet, indigo, blue, green, yellow,
orange, and red, abbreviated as VIBGYOR) are the components of the visible
light. The portions of electromagnetic radiation with wavelengths greater or less
than the wavelengths in the visible light range are invisible to the human eye.
From here onward, the word “light” will be used to represent electromag-
netic radiation (regardless of whether it is visible or invisible to the human
eyes). The speed of light in vacuum is a constant, 2.99792458 × 108 m⋅s−1.
Wavelength and frequency of a light wave are related through Equations 1.1
and 1.2. The different wavelength ranges of electromagnetic radiation consti-
tute different portions of the electromagnetic “spectrum.” Selected portions
of electromagnetic spectrum and their names are summarized in Table 1.1.
Wavelength is expressed in nanometers (nm) for the ultraviolet–visible
region and micrometers (μm) for the infrared region. Wavenumber is usually
expressed in cm−1. For example, a light wave with 200-nm wavelength rep-
resents ultraviolet light and corresponds to a wavenumber of 50,000 cm−1
 1 
 = 50, 000 cm−1  and a frequency of 1.5 × 1015 Hz
cm
 200 × 10−9 m × 100 
 m 
 cm 
 50, 000 cm−1 × 2.99792458 × 1010 = 1.5 × 1015 s−1  .
 s 
TABLE 1.1
Selected Regions of Electromagnetic Radiationa,b
Energy, E
Region Wavelength, λ Wavenumber, ν Frequency, ν (Hz) (kJ/mol)
Ultraviolet 200–400 nm 50,000–25,000 cm−1 1.5 × 1015–0.75 × 1015 598–299
Visible 400–800 nm 25,000–12,500 cm−1 0.75 × 1015–0.37 × 1015 299–150
Near-infrared 0.8–3 μm 12,500–3,333 cm −1 0.37 × 10 –0.1 × 10
15 15 150–39.9
Mid-infrared 3–25 μm 3,333–400 cm−1 1.0 × 1014–0.1 × 1014 39.9–4.78
Far-infrared 25–100 μm 400–10 cm−1 12 × 1012–3 × 1012 4.78–1.20
a 1 nm = 10 m; 1 μm = 10 m; ν = 1/λ; ν = c/λ; speed of light, c = 2.99792458 × 1010 cm/s;
−9 −6
energy per photon is E = hc/λ; Planck’s constant, h = 6.62606896 × 10−34 J⋅s−1; kJ = 1,000 J; cal
= 4.184 J; energy per mole of photons is E = Nhc/λ, where N is the Avogadro’s number;
N = 6.02214179 × 1023 mol−1.
b Wavelengths are expressed in nanometer for the ultraviolet–visible region and micrometer for
the infrared region. Wavenumbers are expressed in cm−1.
1.2 Polarization States

An electromagnetic wave is associated with electric and magnetic fields
oscillating perpendicular to each other. Waves are represented in three
mutually perpendicular Cartesian axes x, y, and z. In a right-handed coordi-
nate system, the thumb, index, and middle fingers of right hand represent,
respectively, the x, y, and z axes (see Figure 1.2). If an electromagnetic wave
is represented to propagate along the z axis, then electric and magnetic fields
will be oscillating in the two perpendicular xz and yz planes containing
this z axis. For the sake of simplicity, we will restrict our discussion, in this
chapter, to the electric field alone. If light is represented to propagate along
z axis, with its electric field oscillating in the xz plane, then light is said to be
x-polarized or linearly polarized along the x axis or plane polarized in the
xz plane. If light is represented to propagate along the z axis, with its electric
field oscillating in the yz plane, then light is said to be y-polarized or linearly
polarized along the y axis or plane polarized in the yz plane. If the electric
field is represented to oscillate arbitrarily in the planes containing the z axis,
then that light is said to be unpolarized. Optical devices, known as polariz-
ers, are used to select a desired polarization. Also the optical devices known
as polarization rotators are used to rotate the linear polarization to a desired
orientation.
Two or more waves that have the same frequency and the same relation-
ship between corresponding points at all times are referred to as coherent
waves. Coherent light waves are normally realized by taking a parent light
wave from a given light source and resolving it into component waves. More
details on how to realize the x- and y-polarized coherent light components
are given later. By combining the x-polarized and y-polarized coherent light
wave components, one can generate a variety of polarization states. First,
let us consider an x-polarized wave component propagating in time t, along
y
e yz plane
x xy plan
z
2
4 3
1
=
FIGURE 1.2
The x-polarized cosine wave with unit amplitude, cosΘ t (curve 1 in the xz plane), and the
y-polarized cosine wave with unit amplitude, cosΘ t (curve 2 in the yz plane), both propagating
along the z axis, result in a linearly polarized wave (curve 3) with its plane bisecting the +x and
+y axes. The projection of this linearly polarized wave in the xy plane (shown as curve 4) gives
a straight line at 45° from the +x and +y axes.
Polarized Light 5
z axis, in the xz plane, with maximum amplitude Fx0. This wave Fx is repre-
sented by Equation 1.3:
Fx = Fx 0 cos2 πνt = Fx 0 cosΘt (1.3)
where the abbreviation Θt = 2πνt is introduced. Similarly, a y-polarized wave

component propagating in the yz plane is represented by, Fy = Fy0 cosΘt, where
Fy0 is its maximum amplitude. We can choose the amplitudes to be equal Fx0
= Fy0 = F0. For convenience in depicting, we will use unit amplitudes, that is,
F0 = 1. As shown in Figure 1.2, when the observer looks in to the incoming
waves (into the z axis in right-handed coordinate system), their combination
appears as a light wave whose electric vector oscillates at 45° between the +x
and +y axes, that is, in the xy plane bisecting the +x and +y axes. The projec-
tion of the resulting wave on to the xy plane appears as a diagonal line in the
xy plane. The resulting linearly polarized light is represented by Equation 1.4:
F = F0 (u cosΘ t + v cosΘ t ) (1.4)
where u and v are unit vectors along the x and y axes, respectively. When both
coherent waves in the xz and yz planes are represented by the same function,
cosΘ t, these waves are said to have zero phase difference. Figure 1.2 demon-
strates that two coherent plane-polarized waves, propagating in mutually
perpendicular planes, without any phase difference between them, combine
to result in a wave whose polarization axis is in between those of parent
waves. This observation can be used in reverse to resolve a plane-polarized
electric vector of a given frequency into two mutually perpendicular plane-
polarized electric vectors of the same frequency whose planes are at +45°
and –45° to that of the parent electric vector. This concept is used to generate
two mutually perpendicular coherent plane-polarized electric vectors from
a linearly polarized parent electric vector of a light source. This concept is
used, for example, in polarization division interferometry (Polavarapu 1997).
1.2.1 Dependence on Phase Difference

If the wave in the xz plane is represented by F0 cosΘt and that in the yz plane by
F0 cos(Θt + δ), then these waves are said to have a phase difference of δ. Variation
of this phase difference between 0 and 2π will lead to changes in the polariza-
tion state of the resulting wave. Since 2π corresponds to 360°, a phase difference
between 0 and 2π corresponds to that between 0° and 360°. For the current dis-
cussion, we will introduce δ into the y-polarized wave and write Equation 1.4 as
F = F0 (u cosΘ t + v cos(Θ t + δ)) (1.5)
and evaluate the polarization state of the resulting wave. The polarization
states obtained by varying δ in increments of π /6 are shown in Figure 1.3.
In this figure, the resulting wave and its projection onto the xy plane are
xy plane yz plane
b
a
δ=0 δ = π/6 δ = π/3 δ = π/2
δ = 2π/3 δ = 5π/6 δ = 7π/6

δ=π
δ = 4π/3 δ = 3π/2 δ=5π/3 δ = 5π/6
FIGURE 1.3
Depiction of the changes in the polarization state as a function of phase difference between the
x-polarized and y-polarized cosine waves propagating along the z direction. The phase shift,
δ , introduced into the y-polarized cosine wave is indicated on the figures.
also shown as a function of δ . As already mentioned earlier, the polariza-

tion of the resulting wave at δ = 0 is linear with its polarization axis at
45° from +x and +y axes. It can be seen from Figure 1.3 that for a phase
difference in the range of π /2 > δ > 0, the projection of the resulting wave
acquires an elliptical shape (which is referred to as the polarization ellipse),
and the electric vector rotates in a clockwise direction. This is shown in
Figure 1.3 for two representative situations with δ = π /6 and δ = 2π /6 =
π /3. The long axis of the polarization ellipse is referred to as the major axis
and the one perpendicular to it as the minor axis. Designating the length
of major axis of the polarization ellipse as “a” and that of minor axis as
“b,” the ratio b/a can be seen to increase (from zero at δ = 0) toward 1 as δ
approaches π /2. This process is akin to watching a collapsed rubber bal-
loon being breathed into, where the balloon takes an elliptical shape with
initial breath of air and progresses toward a circle as more air is blown in.
An ellipse collapses into a line along its major axis when the length of the
minor axis becomes zero. Therefore, for δ = 0, as shown in Figure 1.3, the
projected shape (which we called earlier as a straight line) can be viewed as
an ellipse with b = 0. The angle between the major axis of the polarization
ellipse and +x axis is called the azimuth and designated as θ . This angle is
45° for all three cases, δ = 0, π /6, and π /3, discussed earlier.
Polarized Light 7
At δ = 3π /6 = π /2, as shown in Figure 1.3, the projection of the resulting

wave onto the xy plane indicates that its shape becomes circular (lengths of
major and minor axes are equal; i.e., a = b) with the electric vector rotating
in clockwise direction. This polarization state is referred to as right circular
polarization (RCP), and the wave is referred to as right circularly polarized
wave. This right circularly polarized wave is represented by the expression:
FRCP = F0 (u cosΘ t + v cos(Θ t + π / 2)) = F0 (u cosΘ t − v sinΘ t ) (1.6)
The individual wave components with a phase difference of π /2, along
with the resulting RCP wave and its projection onto the xy plane, are shown
in Figure 1.4. The two individual components that lead to this RCP light wave
are said to have a phase difference of π /2. Since one full wave corresponds to
2π , a phase difference of π /2 corresponds to one-quarter wavelength or λ/4.
In other words, if the y-polarized wave in the yz plane is advanced in time,
by λ/4 relative to the x-polarized wave in the xz plane, then the resulting
wave is right circularly polarized.
For phase differences in the range of π > δ > π/2, as shown in Figure 1.3,
the projected shape of the resulting wave distorts from circular (at δ = π/2)
into elliptical, with the electric vector still rotating in a clockwise direction.
However, note that the major axis of the polarization ellipse is now oriented at
135° from +x axis (i.e., between the positive y axis and negative x axis). This ori-
entation is orthogonal to that for π/2 > δ > 0 (where it was at 45° to the +x axis,
i.e., oriented between the positive x axis and positive y axis). Two representative
examples with δ = 2π/3 and 5π/6 are shown in Figure 1.3. The ratio of the length
of the minor axis to the major axis of the polarization ellipse decreases from 1
(at a phase difference of π/2) toward zero as the phase difference approaches π.
At a phase difference of δ = π, as shown in Figure 1.3, the projected shape
of the resulting wave becomes a straight line (equivalent to an ellipse with b
= 0). That means the resulting wave at a phase difference of π is linearly polar-
ized. However, note that the plane of polarization resulting from δ = π is at
135° from the +x axis, that is, between the –xz and +yz planes (while the plane
of polarization at δ = 0 was at 45° from +x axis, i.e., between the +xz and +yz
yz plane xy plane yz plane

y 4
1 x 3
e
x y plan z
=
2
FIGURE 1.4
The x-polarized cosine wave with unit amplitude, cosΘ t (curve 1 in the xz plane), and phase-
shifted (δ = π /2) y-polarized cosine wave with unit amplitude, cos(Θ t + π /2) (curve 2 in the yz
plane), both propagating along the z axis, result in a right circularly polarized wave (curve 3).
The projection of this right circularly polarized wave in the xy plane is shown as curve 4.
planes). Thus, a phase difference of π between the coherent waves propagating

in the xz and yz planes rotates the plane of polarization, around the propagat-
ing z axis, by 90°, from θ = 45° to 135°. Since one full wave corresponds to 2π,
a phase difference of π corresponds to one-half wavelength or λ/2. In other
words, if a y-polarized wave in the yz plane is advanced or shifted forward
in time, by λ/2 relative to the x-polarized wave in the xz plane, then the plane
of polarization of the resulting wave is rotated around the z axis by 90°. This
linearly polarized wave is represented by the following expression:
F = F0 (u cosΘ t + v cos(Θ t + π)) = F0 (u cosΘ t − v cosΘ t ) (1.7)
The individual wave components with a phase difference of π , along with
the resulting electric vector and its projected shape, are shown in Figure 1.5.
Note that a phase difference of –π will give the same result as that for a phase
difference of +π , so the advancing (shifting forward) of the y-polarized wave
or retardation (shifting in reverse) of the y-polarized wave (relative to the
x-polarized wave) by one-half wavelength has the same effect.
For phase differences in the range of 3π /2 > δ > π , as shown in Figure 1.3,
the projected shape of the resulting electric vector acquires an elliptical shape
again, but the electric vector of the resulting wave now rotates in a counter-
clockwise direction. Note that this sense of rotation is opposite to that for
phase differences in the range π > δ > 0. Two representative examples with
phase difference of 7π /6 and 4π /3 are shown in Figure 1.3. The ratio of the
length of the minor axis to the major axis of the polarization ellipse starts out
at zero (at δ = π ) and approaches 1 as the phase difference approaches 3π /2.
At a phase difference of 3π/2, the projected shape of the resulting electric
vector is a circle with its electric vector rotating in a counterclockwise direc-
tion. This polarization state is referred to as left circular polarization (LCP).
This left circularly polarized wave is represented by the following expression:
FLCP = F0 (u cosΘ t + v cos(Θ t + 3 π / 2)) = F0 (u cosΘ t + v sinΘ t ) (1.8)
y
x xy plane yz plane
z
2
1 3
4
=
FIGURE 1.5
phase-shifted (δ = π ) y-polarized cosine wave with unit amplitude, cos(Θ t + π ) (curve 2 in the
yz plane), both propagating along the z axis, result in a linearly polarized wave (curve 3) with
its plane bisecting the −x and +y axes. The projection of this linearly polarized wave in the xy
plane is shown as curve 4.
Polarized Light 9
The individual wave components with 3π /2 phase difference, along with

the resulting LCP wave and its projected shape in the xy plane, are shown in
Figure 1.6. The two individual components that lead to this LCP light wave
are said to have a phase difference of 3π /2. Since one full wave corresponds to
2π , a phase difference of 3π /2 corresponds to three quarters of a wavelength
or 3λ/4. In other words, if a y-polarized wave in the yz plane is advanced or
shifted forward in time along the z axis, by 3λ/4 relative to the x-polarized
wave in the xz plane, then the resulting wave is left circularly polarized. An
alternate way to generate an LCP wave is to slow down the y-polarized wave
by –λ/4 (i.e., introduce a phase difference of δ = –π /2), instead of advancing
it by 3λ/4, relative to the x-polarized wave. This is because F = F0 (u cosΘ t +
v cos(Θ t – π /2)) = F0 (u cosΘ t + v sinΘ t), which is same as Equation 1.8.
For phase differences in the range of 2π > δ > 3π /2, as shown in Figure 1.3,
the projected shape of the resulting electric vector distorts from a circle (at δ
= 3π /2) to an elliptical shape, with the electric vector of the resulting wave
rotating in a counterclockwise direction (as it was between π and 3π /2), but
the azimuth of the polarization ellipse is back to 45° (as it was for the range,
π /2 < δ > 0). Two representative examples with a phase difference of 5π /3
and 11π /6 are shown in Figure 1.3. The ratio of the length of the minor axis
to the major axis of the polarization ellipse decreases from 1 (at δ = 3π /2) and
approaches zero as the phase difference approaches 2π . Note that a phase
difference of 2π is the same as 0 and that beyond 2π the polarization cycle
that we discussed between 0 and 2π repeats itself.
The observations made so far are summarized in Table 1.2 and are also shown
in Figure 1.7 in the form of a “polarization wheel.” This “wheel” has two circles
and two spokes: one vertical spoke that bisects the inner circle and one hori-
zontal spoke that bisects the outer circle. Opposite ends of the vertical spoke
are capped with linear polarizations, and the opposite ends of the horizontal
spoke are caped with circular polarizations. The vertical spoke separates the
light waves that have a clockwise sense of rotation (π > δ > 0) from those that
have a counterclockwise sense of rotation (2π > δ > π). The horizontal spoke
separates the light waves that have an azimuth θ = 45° (π/2 > δ ≥ 0; and 2π ≥ δ
> 3π/2) from those that have an azimuth θ = 135° (3π/2 > δ > π/2). It is useful to
yz plane y xy plane yz plane

2 x 4
z
ane 1
xz pl = 3
FIGURE 1.6
phase-shifted (δ = 3π /2) y-polarized cosine wave with unit amplitude cos(Θ t + 3π /2) (curve 2 in
the yz plane), both propagating along the z axis, result in a left circularly polarized wave (curve
3). The projection of this left circularly polarized wave in the xy plane is shown as curve 4.
TABLE 1.2
Dependence of Resulting Polarization on the Differences in Amplitudes and Phases of
x-Polarized and y-Polarized Coherent Wave Components Propagating in z Direction
Phase Polarization Sense of
Amplitudes Differencea State Rotation θb
Exo = Eyo δ=0 Linear 45°
π /2 > δ > 0 Elliptical Clockwise 45°
δ = π /2 Right circular Clockwise
δ = π > δ > π /2 Elliptical Clockwise 135°
δ=π Linear 135°
δ = 3π /2 > δ > π Elliptical Counterclockwise 135°
δ = 3π /2 Left circular Counterclockwise
δ = 2π > δ > 3π /2 Linear Counterclockwise 45°
Exo > Eyo; Eyo ≠ 0 δ=0 Linear 0 > θ < 45°
Exo < Eyo; Exo ≠ 0 δ=0 Linear 90° > θ > 45°
Exo > Eyo; Eyo ≠ 0 δ = π /2 Elliptical Clockwise 0°
Exo < Eyo; Exo ≠ 0 δ = π /2 Elliptical Clockwise 90°
a Phase δ is introduced into the y-polarized component.
b θ, referred to as the azimuth, is between the +x axis and the major axis of the polarization ellipse.
Linear polarization can be viewed as a special case of elliptical polarization by collapsing the
ellipse so that its minor axis vanishes and its major axis becomes the linear polarization axis.
Linear
δ = 0 or 2π
θ = 45º
Counterclockwise
Clockwise
Left circular, δ = 3π/2 δ = π/2, Right circular
θ = 135º
δ=π
Linear
FIGURE 1.7
A “polarization wheel” summarizing the polarization states generated by two orthogonal
plane-polarized coherent cosine waves of equal amplitudes as a function of the phase differ-
ence between them.
remember that the sense of rotation for the polarization vector changes when-
ever the polarization state goes through a linear polarization, while the azimuth
changes whenever the polarization state goes through a circular polarization.
From the earlier paragraphs, it can be seen that right and left circularly
polarized light waves can be generated from two plane-polarized coherent
Another random document with
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The plant called “life everlasting” is one which grows in dry, open,
sunny places. It clothes its leaves with silky hairs, and so prevents
them from throwing off too quickly the small amount of water its roots
are able to provide. Without this silky coat, the sun would suck its
leaves quite dry of water.
Sometimes a leaf has only a few of the little leaf mouths through
which most of the water passes. As these mouths are wide open
only in the sunlight, and as often the rest of the leaf is covered with a
thick skin which prevents the water from slipping away (as a little of it
nearly always does) through the cell walls, such a leaf will hold its
water supply and keep fresh for a long time. Such leaves as these
we find on what we call “evergreen” plants. The pines and hemlocks
which light up the woods all winter have these thick-skinned, few-
mouthed leaves, which throw off so little water that even when the
ground is frozen hard, and gives no drinking water to the roots, they
are able to keep fresh by the careful way in which each one hoards
its own little supply.
WOOLLY AND “DUSTY” LEAVES
C URIOUSLY enough, some plants put on a hairy coat for just the
opposite reason from the one which makes life everlasting
clothe itself in that fashion. Life everlasting fears lest its leaves throw
off their water, or perspire too quickly.
Down by the stream that runs through the meadow grow great
clusters of the pink-flowered steeple bush. If you look at the lower
sides of the leaves of the steeple bush, you see that they are very
woolly. As this wool is not between the sun and the leaf blade, it
cannot be meant to protect the leaves from the heat of the sun; and
indeed in this wet meadow, close to the river, never mind how quickly
the leaves throw off their water, the roots can have no difficulty in
finding close by more than enough to make good the loss. No, the
fact is that these leaves need to throw off water very freely indeed to
make room for the ever-fresh supply that is pushing up the stem, and
their woolly covering is intended to help them do this very thing. Its
object is to aid perspiration. In swampy places the moisture rises
every night from the wet ground, and settles on the plants about. The
little mouths on the under surfaces of the leaves of the steeple bush
would soon be clogged with the moisture rising from below, if they
were not protected in some way; and if they became so clogged,
they could not throw off the water with which the whole plant is
charged. Thus, by having this thick coat of hair, the water that
otherwise would cling to the outer surface of the leaf blade is kept at
a distance from the little mouths, and these are not interrupted in the
performance of a duty so necessary to the health of the plant.
This same habit of coating its lower leaf surfaces with hair, you
notice in the speckled or swamp alder, a shrub which grows also in
wet places, and therefore runs the same risk of having its leaf
mouths clogged with water.
So when you see only the upper surface of a leaf covered with
hair, you can guess that the object of the plant is to prevent too much
perspiration; but when you see only its lower side clothed in this
same way, you can guess that the plant fears too little perspiration.
Sometimes you find a plant with leaves which have a coating of
what looks almost like dust on one or both of their surfaces. This
dust we call “bloom.” We see it in apples and grapes, as well as on
leaves. It is made up of a waxy material which is put forth by the
plant just as it puts forth hair. This bloom the plant uses also as a
help to free perspiration. By thus clothing its leaves it shields the little
mouths from water clogging; and so you can be sure that the little
mouths have not been filled with water, and thus prevented from
doing their work.
The cabbage leaf has mouths on both of its surfaces, and so both
sides are covered with this protecting bloom. If you dip a cabbage
leaf in water and then shake it, the drops roll off and leave it quite
dry.
PRICKLES AND POISON
L EAVES need to protect themselves from other enemies than too

great heat and too much water.
We found that the prickly armor of the thistle enabled it to live in
pastures where the cattle had killed most of the other plants.
Many animals like to eat green leaves, so we are not surprised to
find that plants invent different ways of protecting themselves.
One look at the leaf of the thistle is enough to persuade us that it
would not be very good eating.
The red-berried holly, with which we decorate our churches and
houses at Christmas time, is another plant with prickly leaves.
Some plants cover their leaves with bristles, which the cattle dread
almost as much as the stout prickles.
As we read before, the mullein defends its leaves by a fuzzy coat
of hair. Such an armor as this is less warlike than that of the thistle,
but quite as effective.
Other plants fill their leaves with juices which are either poisonous
or unpleasant.
It seems as if animals guessed the presence of these unfriendly
juices by the plant’s smell, for they will munch the different growing
things all about such a plant as this, and leave the harmful leaves
severely alone.
The nettles cover their leaves with stinging hairs. These stiff hairs
break off when handled, burying themselves in the flesh, and
sending out a burning acid that punishes severely the meddler, man
or beast, as it may happen to be.
By this time I think you realize that leaves are well worth noticing.
And when you have looked at a leaf so fully as to be able to carry in
your mind its outline, I hope you will then discover whether it wears a
coat of hair, or a dusty bloom, or a prickly armor, or a thick,
evergreen skin, and that you will decide what enemies it is trying to
escape.
SOME CRUEL TRAPS
H AVE you ever seen a leaf like the one in this picture (Fig. 152)?
It is shaped something like a pitcher; and the plant on which it
grows has been named the “pitcher plant.”
Fig. 152
The pitcher plant lives in low, wet place, such as the shaded
swamp, or the marsh down by the lake.
On account of its curious leaves it is brought to the cities, and is
sold on the street corners or at the florists’.
In June comes the great flower of the pitcher plant. Sometimes
this is a dull red; again it is a delicate pink or perhaps a light green;
and it has faint, pleasant fragrance.
Next June I hope that some of you children will find these beautiful
flowers and these curious leaves.
Why should a leaf be shaped like a pitcher, do you suppose?
These leaves are not only pitcher-like in shape, but also in their
way of holding water; for if you succeed in discovering a settlement
of pitcher plants, you will find that nearly every pitcher is partly filled
with rain water. Usually this water is far from clear. It appears to hold
the remains of drowned insects; and sometimes the odor arising
from a collection of these pitcher plants is not exactly pleasant.
Perhaps you wonder how it happens that dead insects are found
in every one of these pitchers; and possibly you will be surprised to
learn that apparently these curious leaves are built for the express
purpose of capturing insects.
It is easy to understand that these odd leaves are not so well fitted
as more simple ones to cook the plant’s food in the sun, or to take
carbon from the air; but if they are unfitted to provide and prepare
ordinary food, possibly they are designed to secure food that is
extraordinary.
It seems likely that the pitcher plant is not content to live, like other
plants, upon the simple food that is taken in from the earth and from
the air. We are led to believe that it wishes something more
substantial; that it needs a meat diet; and that to secure this, it
teaches its leaves to capture flies and insects in order that it may
suck in their juices.
These leaves are veined in a curious and striking fashion. The
bright-colored veins may convince the insects of the presence of the
sweet nectar in which they delight. At all events, in some way they
are tempted to enter the hollow leaf; and, once they have crawled or
tumbled down its slippery inner surface, they find it impossible to
crawl back again, owing to the stiff hairs, pointing downward, which
line the upper part of the pitcher.
Even if they have wings, it is difficult for them to fly upward in so
straight a line as would be necessary to effect their escape.
When tired out in their efforts to get out of this cruel trap, they fall
into the water at the bottom of the pitcher, and are drowned. Their
bodies decay and dissolve; and it is thought that this solution is
taken in by the leaf, and turned over to the plant as food.
It is just the old, sad story of the spider and the fly, you see, only
now it is the pitcher and the fly.
But be sure to examine one of these pitchers if you possibly can,
and then you will understand better how the whole thing is managed.
The leaf in this picture (Fig. 153), for it is a leaf, you cannot find in
our North American swamps. It grows on a plant called Nepenthes, a
plant which lives in hot countries far from the United States.
Fig. 153
The leaf in the picture is full grown, and all ready for its work of
trapping animals. Before it was old enough to do this, the lid which is
now lifted was laid nicely across the opening to the pocket, and so
prevented any unseasonable visits.
Sometimes these pockets are so large as to be able to hold and to
hide from sight a pigeon. They are gayly colored, and the rim around
their border is covered with a sugary, tempting juice. So you can
guess that the animals in search of nectar are not slow in accepting
the invitation offered by color and sweets, and that some of these
are imprudent enough to venture across the sticky edge. In this
event they are pretty sure to lose their footing on the slippery inner
surface of the pocket, and to fall into the watery liquid with which it is
filled. Even if they do not slip immediately, their efforts to crawl back
over the rim are defeated by a row of teeth such as you see in the
picture.
The liquid at the bottom of the leaf is not rain water, as in the
pitcher plant. It is given out by the leaf itself; and it contains an acid
which dissolves the animals’ bodies, so that their more nourishing
parts can easily be taken in by certain little cells which line the lower
part of the pocket, and which have been brought up to this work.
Fig. 154
The next picture (Fig. 154) shows you a water plant. It is called the
“bladderwort,” because of the little bags or bladders which you see
growing from the branches under water. The little bladders are traps
set for water animals, which swim into them in their wish, perhaps, to
escape some enemy. But they are quite unable to swim out again;
for the door into the bladder is transparent, and looks like an open
entrance with a nice hiding place beyond. It opens easily from the
outside, but is so arranged that it will not open from within. So when
the poor little animal hurriedly swims into what seems to it a cozy
resting spot, and draws a long breath of relief at getting safe inside, it
is hopelessly caught, and must slowly starve to death, for there is no
chance of escape. It may live for nearly a week in this prison; but at
last it dies. Its body decays, and is taken in as food by the cells set
apart for that purpose.
Strangely enough, though we ourselves do not hesitate to kill
animals for food, and sometimes, I am sorry to say, for nothing but
amusement, we give a little shiver of disgust when we find these
plants doing the same thing. Some lines that came out in one of the
magazines a few years ago express this feeling:—
“What’s this I hear

About the new Carnivora?
Can little plants
Eat bugs and ants
And gnats and flies?
A sort of retrograding!
Surely the fare
Of flowers is air,
Or sunshine sweet.
They shouldn’t eat
Or do aught so degrading.”
MORE CRUEL TRAPS
T HE plants about which we read in the last chapter do not take

any active part in capturing insects. They set their traps, and
then keep quiet. But there are plants which lay hold of their poor
victims, and crush the life out of them in a way that seems almost
uncanny.
This leaf (Fig. 155) belongs to a plant which lives in North
Carolina. It is called Venus’s flytrap.
Fig. 155
You see that the upper, rounded part of the leaf is divided by a rib
into two halves. From the edges of these rounded halves run out a
number of long, sharp teeth; and three stout bristles stand out from
the central part of each half. When an insect alights upon this
horrible leaf, the two halves come suddenly together, and the teeth
which fringe their edges are locked into one another like the fingers
of clasped hands.
The poor body that is caught in this cruel trap is crushed to pieces.
Certain cells in the leaf then send out an acid in which it is dissolved,
and other cells swallow the solution.
After this performance the leaf remains closed for from one to
three weeks. When finally it reopens, the insect’s body has
disappeared, and the trap is set and ready for another victim.
The next picture (Fig. 156) shows you a little plant which is very
common in our swamps,—so common that some of you ought to find
it without difficulty next summer, and try upon it some experiments of
your own.
Fig. 156
It is called the “sundew.” This name has been given to it because

in the sunshine its leaves look as though wet with dew. But the pretty
drops which sparkle like dew do not seem so innocent when you
know their object. You feel that they are no more pleasing than is the
bit of cheese in the mouse trap.
When you see this plant growing in the swamp among the
cranberry vines and the pink orchids, you admire its little white
flowers, and its round red-haired leaves, and think it a pretty,
harmless thing. But bend down and pluck it up, root and all, out of
the wet, black earth. Carry it home with you, and, if you have a
magnifying glass, examine one of its leaves.
The picture (Fig. 157) shows you a leaf much larger than it is in
life. The red hairs look like pins stuck in a cushion, and the head of
each pin glistens with the drop that looks like dew.
Fig. 157
But the ants and flies do not take these drops for dew. They
believe them to be the sweet nectar for which they long, and they
climb or light upon the leaves in this belief.
And then what happens?
The next two pictures will show you (Figs. 158, 159).
Fig. 158
Fig. 159
The red hairs close slowly but surely over the insect whose legs
are already caught and held fast by the sticky drops it mistook for
nectar, and they hold it imprisoned till it dies and its juices are
sucked in by the leaf.
I should like you to satisfy yourselves that these leaves act in the
way I have described. But a bit of fresh meat will excite the red hairs
to do their work quite as well as an insect, and I hope in your
experiments you will be merciful as well as inquiring.
So you see that the little sundew is quite as cruel in its way as the
other insect-eating plants. But its gentle looks seem to have
deceived the poet Swinburne, who wonders how and what these
little plants feel, whether like ourselves they love life and air and
sunshine.
“A little marsh-plant, yellow-green

And tipped at lip with tender red,
Tread close, and either way you tread,
Some faint, black water jets between
Lest you should bruise its curious head.
“You call it sundew; how it grows,

If with its color it have breath,
If life taste sweet to it, if death
Pain its soft petal, no man knows,
Man has no sight or sense that saith.”
THE FALL OF THE LEAF
Y OU know that in autumn nearly all the leaves fall from the trees.
To be sure, a few trees (such as the pines and hemlocks) and
some plants (such as the laurel and wintergreen and partridge vine)
do hold fast their leaves all winter; but these are so few as compared
with the many plants which lose their leaves, that they hardly count.
Perhaps you never stopped to wonder why most plants get rid of
their leaves before winter comes on; but you feel pretty sure now
that there is some good reason for a habit that is adopted by nearly
all the plants that live in this part of the country.
When we were talking about the way in which leaves defend
themselves from different dangers, we found that evergreen leaves,
the leaves which hold fast to the tree and keep fresh all winter,
manage to keep their water safe inside their cells by wearing a very
thick skin, and by not having too many little leaf mouths. For when a
leaf has a thin skin and a great many mouths, its water leaks away
very quickly. And if many such leaves should remain upon a plant
into the winter, might it not happen that they would let off all its water
at a time when its roots could not find any more in the frozen
ground? And thus might not the leaves kill the plant by draining it
quite dry?
So you can see why it is well for most plants to shed their leaves
before winter comes on and the root’s drinking water is turned into
ice.
But when a plant is about to shed its leaves, it takes care not to
waste the precious food which they hold. This food it draws back into
its stem and roots, laying it away in safe places beneath the buds
which are to burst another year.
It is this action on the part of the plant which changes the color of
the leaves every fall. That material which makes them green is
broken up, and part of it is taken away. That which is left is usually
yellow or brown or reddish, and gives the leaves the beautiful colors
we see in our October woods.
So whenever you see the woods changing color, losing their fresh
green and turning red and yellow, you can be sure that the trees
have begun to prepare for winter. You know that they are stowing
away their food in warmer, safer places than can be supplied by the
delicate leaves. And when all the food has been drawn out of the
leaves, and packed away in the right spots, then the plant finishes a
piece of work it began some time before. This piece of work is the
building-up of a row of little cells just where the leafstalk joins the
stem or branch. When this row is complete, it acts almost like a
knife, loosening the stalk from the stem.
Then the leaf’s life work is over; and with the first breeze, the
empty shell, which is all that is left, breaks away from the parent
plant, and drifts earthward.
Part VI—Flowers
THE BUILDING PLAN OF THE CHERRY

BLOSSOM
O NE day your teacher brought to school a branch broken from

the cherry tree. This she placed in water, standing the tumbler
on the sunny window sill; and now its buds have burst into a glory of
white blossoms.
To-day I want you to study the flower of the cherry; for if you know
all about this flower, which is put together in a rather simple way, one
that is easy to study, it will not be so difficult for you to understand
other, less simple flowers.
You may wonder why I do not wait till the cherry tree outside is in
blossom; but if we waited till May, other flowers, which are not built
on quite so simple a plan, would have come and gone, and you
would not have been able to understand them so well as if you had
first studied the simple make-up of the cherry blossom.
Last fall we learned a little about this flower, but we had only its
picture to help us in our work: so I think it well to begin all over again.
In looking at the cherry blossom (Fig. 160), we should first notice
the green cup which holds the rest of the flower.
This cup is divided into five green leaves.
During the babyhood of the flower, when it was quite too young to
face the cold, windy world, these green leaves were folded together
so as to shut away from all harm its more delicate parts.
Above this green cup we see a circle made up of five white leaves.
These pretty leaves are spread outward as if they were quite proud
of themselves, and eager to attract attention.
And that is just what they are trying to do; for the cherry blossom is
not wise enough to know that here in the schoolroom there are no
bee visitors to bring it yellow dust, and to help it grow into a cherry.
These leaves are the little handkerchiefs which the cherry tree, just
like the apple tree we read about long ago, uses in signaling the
bees.
Fig. 160
Within the circle of white leaves you see a quantity of what we

named “pins with dust boxes.” You remember that these dust boxes
hold the powdery material which is as wonderful as Cinderella’s fairy
godmother in its power to do strange and surprising things.
And in the very center of the flower you find a single “pin,” as we
called it, with a flat top which is not a dust box.
But you remember that at the foot of this pin is another sort of box,
a seedbox (Fig. 161).
And you have not forgotten that it is on the flat top of this pin that
the bee brushes the yellow dust which gives new life to the seed
below, and turns the little case of the seedbox into the juicy cherry.
So now what do we find in the cherry blossom? We find
1. A green cup cut above into separate leaves.
2. A circle of white leaves.
3. Some pins with dust boxes.
4. One pin with a seedbox.
Fig. 161
Here you have the plan on which the cherry blossom is built (for
flowers, like houses, are built on different plans), and the building
plan of the cherry blossom is one of the simplest of all. So it is well,
before studying more difficult flowers, to feel quite at home with this
one. And you must try to remember first what work each part of the
flower is expected to perform; for you see that the leaves of the
green cup, the pretty white leaves, the pins with dust boxes, and the
pin with a seedbox, have each and all their special task,—a task
which they alone are able to accomplish.
Now, in talking about a flower it is troublesome to use a great
many words where one would answer every purpose, so I will tell
you what these different parts of the flower have been named; and
by taking a little trouble to remember these names, we can save a
good deal of time.
The green cup is called the “calyx.”
“Calyx” is a Greek word meaning “cup.”
The circle of leaves which grow above the green cup or calyx is
called the “corolla.”
“Corolla” comes from a word which means “crown.”
The pins with dust boxes are called “stamens.”
“Stamen” comes from a word meaning “to stand.”
The pin with a seedbox is called the “pistil.”
“Pistil” is another form of the word “pestle.” A pestle is an
instrument used in the drug shops for pounding and mixing
medicines. You might ask to look at one the next time you are sent to
the drug shop, and then you can see for yourselves if it really looks
like its namesake, the pin with a seedbox.
Perhaps at first you may find it a little difficult to bear in mind these
four words with their meanings; but soon they will become quite
easy, and will save you much trouble.
Green cup,—calyx.
Circle of flower leaves,—corolla.
Pins with dust boxes,—stamens.
Pin with seedbox,—pistil.
If you remember the names of these four parts of the flower, how
the different parts look, and what they do, you will have made a good
start in the study of flowers.

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Chiroptical spectroscopy:

fundamentals and applications 1st

X Ray Spectroscopy with Synchrotron Radiation

EPR Spectroscopy Fundamentals and Methods 1st Edition

Fundamentals and Applications of Heavy Ion Collisions

Fracture Mechanics: Fundamentals and Applications,

Molecular Spectroscopy, Second Edition Jeanne L. Mchale

Fundamentals of Sum Frequency Spectroscopy 1st Edition

Nanostructures for Antimicrobial and Antibiofilm

Applications of EPR and NMR spectroscopy in homogeneous

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International Standard Book Number-13: 978-1-4200-9246-2 (Hardback)

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Names: Polavarapu, Prasad L.

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1. Polarized Light ................................................................................................1

3. Interaction of Circularly Polarized Light with Chiral Molecules ...... 37

4. Quantum Chemical Formulation of Chiroptical Spectroscopy..........57

4.3 Time-Dependent Perturbation Theory ............................................ 66

5. Prediction of Chiroptical Spectra..............................................................89

5.3.3 Vibrational Circular Dichroism ......................................... 111

7.7 Summary ............................................................................................ 165

8. Comparison of Experimental and Calculated Spectra ....................... 175

9. Chiral Aggregation, Equilibria, and the Horeau Effect .....................197

10. Applications of Chiroptical Spectra .......................................................221

10.2.3 VCD Spectra.......................................................................... 230

A1. Polarization States and Stokes Parameters ........................................... 317

A2. Kramers–Kronig Transformation ...........................................................323

A3. Spectral Simulations .................................................................................. 327

A5. Averaging Properties Using Boltzmann Populations .........................363

A6. Monochromators and Interferometers ...................................................367

A7. Polarization Modulation ...........................................................................373

A8. Units and Conversions ..............................................................................385

A8.10 Conversion of Dipole Strength to Absorption Intensity in

Optical activity is a phenomenon that is well known to scientists (chemists,

impossible to achieve these goals in one monograph. Nevertheless, I tried to

Prasad L. Polavarapu, PhD, was born and raised in Gudlavalleru, a small

Interaction between electromagnetic radiation and matter is the basis of a

1.1 Introduction to Light

1.2 Polarization States

Fx = Fx 0 cos2 πνt = Fx 0 cosΘt (1.3)

where the abbreviation Θt = 2πνt is introduced. Similarly, a y-polarized wave

F = F0 (u cosΘ t + v cosΘ t ) (1.4)

1.2.1 Dependence on Phase Difference

F = F0 (u cosΘ t + v cos(Θ t + δ)) (1.5)

δ=0 δ = π/6 δ = π/3 δ = π/2

δ = 2π/3 δ = 5π/6 δ = 7π/6

δ = 4π/3 δ = 3π/2 δ=5π/3 δ = 5π/6

also shown as a function of δ . As already mentioned earlier, the polariza-

At δ = 3π /6 = π /2, as shown in Figure 1.3, the projection of the resulting

yz plane xy plane yz plane

planes). Thus, a phase difference of π between the coherent waves propagating

The individual wave components with 3π /2 phase difference, along with

yz plane y xy plane yz plane

Left circular, δ = 3π/2 δ = π/2, Right circular

L EAVES need to protect themselves from other enemies than too

“What’s this I hear

T HE plants about which we read in the last chapter do not take