Nonlinear Optical Polarization Analysis in Chemistry and Biology

498 Pages·2017·5.416 MB·English

by  Garth J. Simpson

NONLINEAR OPTICAL POLARIZATION ANALYSIS IN
CHEMISTRY AND BIOLOGY
This rigorous yet accessible guide presents a molecular-based description of non-
linearopticalpolarizationanalysisofchemicalandbiologicalassemblies.Itincludes
discussion of the most common nonlinear optical microscopy and interfacial meas-
urements used for quantitative analysis, specifically second harmonic generation
(SHG), two-photon excited fluorescence (2PEF), vibrational sum frequency gener-
ation (SFG), and coherent anti–Stokes Raman spectroscopy/stimulated Raman
spectroscopy(CARS/SRS).Alinearalgebramathematicalframeworkisdeveloped,
allowing stepwise systematic connections to be made between the observable
measurements and the molecular response. Effects considered include local field
corrections; the molecular orientation distribution; rotations among the molecular
frame,thelocalframe,andthelaboratoryframe;andsimplificationsfrommolecular
and macromolecular symmetry. Specific examples are provided throughout the
book, working from the common and relatively simple case studies through to the
most general scenarios.
garth j. simpson is Professor in the Department of Chemistry at Purdue
University. He has co-authored more than 100 articles and given over 100
invited lectures on nonlinear optics and related phenomena. He is the recipient of
numerous honors, including the Research Innovation Award from the Federation
of Analytical Chemistry and Spectroscopy Societies, the Findeis and Victor
K. LaMer Awards from the American Chemical Society, a Cottrell Teacher-
Scholar Award from the Research Corporation, and a Beckman Young Investi-
gator Award.
CAMBRIDGE MOLECULAR SCIENCE
Aswemovefurtherintothetwenty-firstcentury,chemistryispositioningitselfasthecentralscience.
Itssubjectmatter,atomsandthebondsbetweenthem,isnowcentraltosomanyofthelifesciences
on the one hand, as biological chemistry brings the subject to the atomic level, and to condensed
matter and molecular physics on the other. Developments in quantum chemistry and in statistical
mechanics have also created a fruitful overlap with mathematics and theoretical physics. Conse-
quently, boundaries between chemistry and other traditional sciences are fading and the term
MolecularSciencenowdescribesthisvibrantareaofresearch.
Molecular science has made giant strides in recent years. Bolstered both by instrumental and
theoreticaldevelopments,itcoversthetemporalscaledowntofemtoseconds,atimescalesufficient
to define atomic dynamics with precision, and the spatial scale down to a small fraction of an
Angstrom. This has led to a very sophisticated level of understanding of the properties of small
molecule systems, but there has also been a remarkable series of developments in more complex
systems.Theseincludeproteinengineering,surfacesandinterfaces,polymers,colloids,andbiophys-
ical chemistry. This series provides a vehicle for the publication of advanced textbooks and
monographsintroducingandreviewingtheseexcitingdevelopments.
SeriesEditors
ProfessorRichardSaykallyUniversityofCalifornia,Berkeley
ProfessorDavidKingUniversityofCambridge
NONLINEAR OPTICAL POLARIZATION
ANALYSIS IN CHEMISTRY AND
BIOLOGY
GARTH J. SIMPSON
PurdueUniversity
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Title:Nonlinearopticalpolarizationanalysisinchemistryandbiology/GarthJ.Simpson.
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Description:Cambridge,UnitedKingdom;NewYork:CambridgeUniversityPress,2016.
|Series:Cambridgemolecularscience|Includesbibliographicalreferencesandindex.
Identifiers:LCCN2016019205|ISBN9780521519083(hardback:alk.paper)
Subjects:LCSH:Polarization(Light)|Nonlinearoptics.|Physicaloptics.|Chemistry.|Biology.
|MESH:Microscopy,Polarization–methods|OpticalProcesses|NonlinearDynamics
Classification:LCCQC441.S562016|NLMQH212.P6|DDC542/.87–dc23LCrecord
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Contents
List of Contributors page vii
List of Terms viii
1 Introduction 1
2 The Molecular Nonlinear Polarizability 17
3 Visualization of the Molecular Tensor 38
4 NLO Properties of Coupled Oscillators and Crystals 49
5 Second-Order Nonlinear Optical Properties of Proteins 74
6 Surface SHG and SFG 93
7 Chirality in Nonlinear Optics 129
8 Nonlinear Optical Ellipsometry 149
9 Bridging the Local to Laboratory Frames in SHG and
SFG Microscopy 184
10 Polarization-Dependent CARS/SRS/Raman Microscopy 227
11 Hyper-Rayleigh Scattering 270
12 Polarization-Dependent Single- and Multi-Photon Excited
Fluorescence of Isotropic Assemblies 281
13 1PEF and 2PEF from Uniaxial Interfaces 317
14 1PEF and 2PEF Microscopy 347
15 Mueller Tensors 392
v
vi Contents
A.1 Rotation Matrix Conventions for Intrinsic vs. Extrinsic Rotation 435
A.2 SHG and SFG Character Tables for Molecules and Crystals 437
A.3 Populating Sparse Matrices in SFG, SHG, and 2PEF
Polarization Analysis 442
A.4 Populating Sparse Matrices in FWM Polarization Analysis 459
A.5 Orientational Averages for Four-Wave Mixing of
Uniaxial Assemblies 463
A.6 Identity Relations for Vectorization of Matrices and Tensors 475
Index 483
Contributors
Nathan J. Begue (Chapter 8)
Azhad U. Chowdhury (Chapters 2 and 11)
Christopher M. Dettmar (Chapter 9)
Emma L. DeWalt (Chapters 5 and 9)
Janny Dinh (Chapters 2 and 4)
Ximeng Y. Dow (Chapter 14)
Levi M. Haupert (Chapters 2, 3, 4, 5, and 7)
Jeremy T. Madden (Chapter 8)
Ryan D. Muir (Chapter 6)
Justin A. Newman (Chapters 4 and 6)
Sreya Sarkar (Chapter 11)
Nicole M. Scarborough (Chapter 7)
Paul D. Schmitt (Chapters 1, 8, and 12)
Garth J. Simpson (Chapters 1–15)
Ximeng You (Chapter 3)
vii
Terms
γ Angle difference between the transition moment and the
nearest plane generated from the principal moments of
α(1)
θ Angular spread of a focused Gaussian beam
0
Z Axial position in a focused Gaussian beam
lb Backward coherence length
c
W Beam waist of a focused Gaussian beam
0
N Bulk number density
b
χ (2) Cartesian nonlinear susceptibility tensor
C
σ Chiral-independent squared norm of the tensor
CD Circular dichroism
CARS Coherent anti–Stokes Raman spectroscopy
CATS Coherent anti-Stokes two photon spectroscopy
β Collective set of monomer tensors
tot
k Coupling between i and j modes
ij
σ Cross-correlation of the original tensor and the tensor
corresponding to its mirror-plane image
Γ Damping term
s Detector sensitivity, where n is horizontal or vertically
n
polarized light
ε Dielectric constant
0
DFG Difference frequency generation
Δω Difference in excitation frequencies
ex
αd Displacement angle of chromophore aggregation
NV Electronic π(cid:1)π* transition
1
Η Excitonic Hamiltonian
α(1) First-order linear polarizability
viii
Terms ix
lf Forward coherence length
c
4WM Four-wave mixing
ω nonlinear susceptibility tensor
ω0 Frequency of the local transition i
i
L Fresnel local field factors
βð2Þ Molecular hyperpolarizability tensor for the sum or
(cid:3)
different state
⇀χ0 Full set of 27 local frame tensor elements
l
lG=2 Guoy phase shift
β(2) Hyperpolarizability tensor
H (subscript) Indicates horizontally polarized optical fields
V (subscript) Indicates vertically polarized optical fields
E Input polarization matrix
I Intensity
β Isotropic molecular hyperpolarizability
iso
M Jones matrix describing optical elements
⇀eω Jones vector of light with a frequency of ω
S(+) Lineshape function for sum states under the assumption
of SHG resonance-enhancement
χ Macroscopic isotropic nonlinear susceptibility
iso
F Matrix relating ⇀a to ⇀χ
P Matrix relating (A to ⇀χJ
J
Δ Measure of the relative magnitude of the residual intrin-
chiral
sic chiral response
S Molecular symmetry matrix
⇀
β Molecular tensor (vectorized)
NLO Nonlinear optical
NR Nonresonant contributions
N Bulk number density
b
N Surface number density
s
N.A. Numerical aperture
J Orientation matrix relating laboratory and local frames
D Orientation parameter
p Perpendicular- light polarized perpendicular to the plane
of reflectance
Δ Phase shift between the two perpendicular polarization
components of light imparted by a phase modulator
Amide I Primarily C=O stretching motion at 1800–1600 cm(cid:1)1
Amide II Primarily N–H bending motion at 1600–1500 cm(cid:1)1