597

Index

a Ag20-pyridine 583, 588 ab initio DFT simulations 462 algebraic diagrammatic construction ab initio methods 282, 330, 418, 464 (ADC) 81 ab initio molecular dynamic (AIMD) α-glycine and l-alanine 476–478 approach 173, 191 amides ab initio simulations 471, 487 dipole–dipole interactions and absolute configuration (AC) 171–173, coupling 132 186, 254 electron-donating effect 135 absorption spectrum 33, 87, 91, 92, 95, Gaussian convolution 130 97, 99, 411, 497, 509–511, 518, hydrogen bonding interaction effects 521, 577–579, 580 135 acetic acid 199, 211, 212, 280, 364, 365, Kramers–Kronig transformation 367 130 acetylacetone 219, 220, 222, 229–232, LR-PCM-TD-DFT calculations 289 131 enol 231, 232 nonequilibrium effect 134 acoustic phonons 427 π-π* transition 130 acrylic acid 365, 366 polarization 132 adenine crystal 475, 476, 479 transition energies 135 adenosine 478, 485, 486 amine-metal interaction 557 ad hoc broadening factor 93 amino-hydroxy (AH) 290 adiabatic approximation 49, 62, 69, amino-metal interaction 555 207 amino-oxo (AO) tautomer 290 adiabatic Hessian (AH) model 21, 517 amino wagging frequencies 551, 552 adiabatic model 10 amino wagging vibration 555, 563, 567 adiabatic shift (AS) 10, 517 ammonia 460 adsorbate-substrate interaction 541, Amsterdam Density Functional (ADF) 549 182, 577 adsorption interaction 538, 540, 546, angle-resolved photoemission 551, 555, 560, 565 spectroscopy (ARPES) 443 adsorption models 546 angle-resolved ultraviolet photoelectron

Ag4 cluster 546, 547 spectroscopy (ARUPS) 440 Ag20 cluster 578, 583, 585 anharmonic couplings 17, 201, 203, Ag clusters 554, 562, 577, 580 211, 480, 487 Ag Nanoclusters 577–579 anharmonic effects 173, 186, 187, 228, Ag nanorods 580–582 231, 232, 353, 355, 516

Molecular Spectroscopy: A Quantum Chemistry Approach, First Edition. Edited by Yukihiro Ozaki, Marek Janusz Wójcik, and Jürgen Popp. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2019 by Wiley-VCH Verlag GmbH & Co. KGaA. 598 Index

anharmonic frequencies 17, 186, 337 1,8-bis(dimethylamino)-4,5-dihydroxyn- anharmonic IR spectrum 428 aphthalene 226 anharmonicity 2, 6–8, 14, 16, 17, 147, bis(trifluoromethanesulfonyl)imide 154, 160, 163, 182, 186–187, 191, (H-TFSI) 282 203–212, 234, 253, 257, 353–355, Bloch theorem 465 377, 378, 380, 381, 390, 399, 404, B3LYP-D* functional basis set 481 414, 415, 435, 524, 568 Bohr frequency 499, 502, 506, 507, anharmonic vibrational analysis 365, 509–511 375, 378 Bohr magneton 11 malic acid 369 Boltzmann coefficients 360 aniline (AN) 549 Boltzmann density operator 204, 206 molecular orbitals 550 Boltzmann factor 180, 274, 275 aniline-Ag4 563, 566 Boltzmann population 9, 19 anisotropic contribution 11 Boltzmann-weighted Raman spectrum anisotropic hyperfine coupling tensor 267 11 bond polarity 310–313, 315 annealed scPLA 485 Born–Oppenheimer (BO) anthracene crystal 474, 479 approximation 174, 466, 500 anti-Stokes scattering 498, 502 Born–Oppenheimer molecular aqueous malic acid, FT-NIR spectrum dynamics (BOMD) 329, 330 370 broad bands 120, 126, 337, 567 aromatic amines 539, 540, 546, 549, butyl alcohols, NIRS 361 554, 557, 567 butyric acid 365, 366 aspirin crystals 338–342 asymmetric carbon 254 c atomic axial tensor (AAT) 173, 174 C-Ag bond length 558 atomic polar tensor (APT) 174 autocorrelation function (ACF) 94, Cambridge Structure Database (CSD) 202, 206, 232, 327, 329, 330, 336, 464 337, 428, 440 carboxylic acids 207, 209, 212, 364, 369 Car–Parrinello dynamic simulations b 184 basis set superposition error (BSSE) Car–Parrinello formulation 225 180, 548 Car–Parrinello molecular dynamics Beer–Lambert’s law 173 (CPMD) 173, 226, 329, 331 bending frequencies 147 calculations 334 benzyl moieties 567 simulations 232 benzyl radical 537, 538, 563 Cartesian coordinate system 236, 418, anion 559 460, 467–469 C–C bond length 558 anion-Ag4 566 Berry phase approach 428 C60 crystal 463, 472, 473, 479 β-hydroxy-α,β-unsaturated carbonyl center of mass (COM) 86, 460 compounds 221 channelrhodopsin 100 β-hydroxyketone enols 231 charge mobility 425, 436, 438, 439, binding energy (BE) 548, 551, 560 442, 443, 449, 450 binding interaction 538, 540, 546, 547, charge transfer (CT) transitions 83 549, 551, 553, 555, 560, 564 charge transport properties, OSCs bio-macromolecules 576 425, 449 biospectroscopy 367 chemical enhancement effect 562–565 Index 599 chemical interactions 554, 575, 576, conformational analysis 585 chlorobenzaldehyde 285–286 chemical mechanism (CM) 576, 585, 1,2-dichloroethane 283–285 589 vanillin 286–289 chemisorption interaction 554 conformational diversity chemometric regression vectors 370 electronic circular dichroism chemometrics 369 272–275 chiral recognition, by molecular vibrational spectrum, solvation in spectroscopy 265–269 anharmonic approaches 186 conventional approach 107, 389 ECD 171 conventional nonpolarizable QM/MM ECD and CPL spectra 176–177 approaches 98 electronic structure methods conventional vibrational calculations 179–182 147 environment-induced CD and CPL core-valence (CV) correlation effects activity 184–185 12 matrix-isolation vibrational circular Coulomb force 460 dichroism spectra (MI-VCD) Coulombic dipole interaction 86 183 Coulomb integrals 576 molecule’s electron density 173 coupled cluster singles and doubles quantum mechanical methods 172 (CCSD) method 82 VCD spectra 173–175 coupled cluster theory like CCSD(T) chlorobenzaldehyde 285–286 282 CH3OH 261, 374, 375 crotonic acid 365, 366 CH-stretching oscillators 404, 405, crystalline inorganic semiconductors 414, 415 425 CH2 wagging (ωCH2) 538 crystalline polymers 459 circular dichroism (CD) 3, 171, 172, crystalline TCNQ 430, 432 176, 177, 183, 269–275 crystalline tropolone 343–344 circularly polarized luminescence (CPL) crystal packing 426, 429–431 3, 171, 177 cyclohexanol 360, 363, 377, 378 circularly polarized phosphorescence 177–179 d clamped nucleus (CN) approximation Darling–Dennison resonances (DDRs) 508 8 classical electrodynamics 575 Davydov coupling 207, 208, 211, 212 classical harmonic oscillator 439 denoted degeneracy-corrected PT2 cluster-in-a-liquid model 183, 184 (DCPT2) 8 complete active space perturbation density functional perturbation theory theory 517 (DFPT) 428 complete active space SCF (CASSCF) density functional theory (DFT) 48, 84, 517 82, 179, 329, 358, 459, 508, 516, computational procedure 153 537, 538, 576 condensed-phase optimized molecular calculation 253 potentials for atomistic procedures 227 simulation studies (COMPASS) density matrix renormalization group 428 (DMRG) method 517 configuration interaction (CI) matrix deperturbed VPT2 (DVPT2) 8, 354, 577 358 600 Index

DFT-D* approach 464, 481 substituted aniline 557 1,8-diaminonaphthalene 291–293 electron dynamics, in molecular di-atomic anharmonicity 354 aggregate system dibenzoylmethane enol 229, 230, 232 electron density matrix 48–49 dicarboxylic acid 369 electron dynamics calculation dicyanobenzenes 432, 433 45–46 differential Raman scattering cross energy transfer phenomena 44 section (DRSC) 548, 550 Fock matrix 45 1,2-dihydrobenz[cdi]indazole (DBI) group diabatic Fock scheme 292 Fock matrix 49–50 1,8-dihydro-1,8-naphthalenediimine local excitation and electron filling (3DND) 292 51–52 diluted methanol observable, Fock and density band assignments 357 matrices 50 NIRS 356 time propagation of density matrix, dimethyloxirane 21, 22 in GD representation 51 dioleoylphosphatidylcholine (DOPC) hole–electron pair 44 158 inter/intra molecular charge dipalmitoylphosphatidylcholine (DPPC) migration 44 158 light–electron couplings 44 dipolar plasmon resonances 580 20-mer ethylene system 52, 56 dipole–dipole coupling terms 11 multi configurational time-dependent dipole moment function 411 Hartree–Fock (MCTDHF) displaced harmonic oscillator model schemes 46 498 multi configuration time dependent diverse nonlinear spectroscopic Hartree (MCTDH) method 47 techniques 102 NPTL-TCNE dimer system 53 donor highest occupied molecular solar-light energy conversion 44 orbital (dHOMO) 86 time-dependent configuration double harmonic approximation 29, interaction theory (TDCI) 46 275, 276, 428, 501–503, 508, 516 time-dependent interaction dynamics double-hybrid functionals 13, 358 45 Duschinsky effects 517–519, 521 electronic circular dichroism (ECD) 3, Duschinsky matrix 10, 513, 515 171, 272–275, 515 Duschinsky rotation effects 505, 511 electronic Hamiltonian 80, 434 Dushinsky transformation 9 electronic quadrupole moment 177 dynamic disorder 93, 94, 105, 436, 437 electronic structure methods 61, 71, 179–182 e electronic theory 360, 365, 380 Eckart conditions 411, 465 electron paramagnetic resonance (EPR) Eckart transformation 542 spectroscopy 10 effective unpaired electron (EUPE) 56 electron-phonon coupling 48, 426, electric-dipole transition moment 434–444, 449 (EDTM) 174 on charge tranport 437 electrochemical charge transfer 583–584 local and non-local 434–436 electromagnetic mechanism (EM) molecular size 441 585, 589 in organic semiconductors 439–440 electron donating (ED) in various organic semiconductors groups 549 440–443 Index 601 electron-phonon interaction 425, 426, π–π* transition 138–141 434, 436, 438, 440, 444, 446, 448, Vienna abinitio simulation package 449 (VASP) 123 electron withdrawing (EW) Fermi-resonance coupling constant groups 549 396 substituted aniline 557 Fermi resonances (FRs) 7, 186, 201, environmental coupling 94 203, 211, 396, 401 equation-of-motion coupled cluster field-effect transistors 425 (EOM-CC) approach 81 first order 5, 9, 204, 394, 396, 397, 401, equation of motion coupled cluster 428, 499 method restricted to single and Fn-TCNQ crystals 426, 427, 443 double excitations (EOM-CCSD) charge transport 444 517 low-frequency vibrations 443–449 ethanol 275, 306, 355, 357, 358, 370 F2n-TCNQ crystals, Raman ethylene-Ag4 559 spectroscopy 430 ethyl tert-butyl ether 370 Fock matrix 45, 49, 50, 87 exchange-correlation (XC) functional force constant 13, 17, 19, 31, 226, 227, 54, 83, 179, 464, 518 256, 354, 391, 515, 542, 544–546, excited state energies 62, 80, 81, 86, 94, 551, 553, 567 98, 103–104, 517, 583, 585 formic acid 211–212, 295, 364 excited state intramolecular proton Fourier transform 173, 206, 332, 337 transfer (ESIPT) 224 Franck–Condon (FC) explicit solvent cavity model 369 approximation 9 contributions 503 f overlap integrals 497, 515 far-infrared spectroscopy 460 principle 8, 435 far-ultraviolet (FUV) spectroscopy structure 96 amides 130–136 vibronic couplings 497, 518–521 ATR-FUV spectroscopy 119, Franck–Condon and Herzberg–Teller 123–124 (FCHT) 21, 497 DFT/TD-DFT calculations 122 Frenkel exciton Hamiltonian parameters electronic transition 119, 120, 104 124–141 F2-TCNQ crystals 429, 430, 444 hydrogen bonding 137–142, 355 full-width at half maximum (FWHM) hydrogen bonding and coupling 122 474, 475, 477, 478, 509 linear response scheme (LR-PCM) 122 g Monkhorst–Pack mesh 123 gas-phase 2-(N-ethyl-α-iminoethyl)-4- n-alkanes in liquid and solid phases chloro-5-methylphenol 234 124–129 gauge invariant atomic orbital (GIAO) nylons 120, 136–141 method 177, 234 π-π* transition 120 Gaussian 229 polarizable continuum model (PCM) Gaussian distributions 105 121 Gaussian’s 6-311G(d,p) basis set 481 quantum chemical calculations 119 generalized (GVPT2) 354, 358 Rydberg transitions 120, 121, 125, GENeralized-Ensemble SImulation 126, 139 System (GENESIS) 148 SAC-CI 120–123, 125, 126, 133, generalized internal coordinates (GICs) 134 10 602 Index

Gibbs free energies 547 higher overtone 378, 379, 411, 412 glycine crystal 477, 479 highest occupied molecular orbital Gram–Schmidt process 81 (HOMO) 52, 86, 88, 343, 344, ground state electronic-adiabatic 549, 566 polarizability 81, 501–503, 508 high-mobility OSCs 426, 443, 449 ground state electronic polarizability high-temperature (HT) 442, 443 502, 503, 508 4H-imidazole ligand 521, 523 ground state equilibrium geometry Holstein–Peierls Hamiltonian 435 502, 504, 517 Holstein-type electron-phonon coupling G16 software 23 435 hybridization effect 537, 540 h hybrid molecular dynamics (QM/MM) half-width at half-maximum (HWHM) 329, 331 483 hydration 160–163 harmonically coupled anharmonic hydrogen-bonded crystals oscillator (HCAO) model 394 applications harmonic approximation 17, 29, 163, ab initio molecular dynamics 174, 176, 226–228, 505, 541, 543, simulations 332 548 aspirin crystals 338–342 harmonic force field (HFF) 12, 21, 30, Car–Parrinello molecular 174 dynamics simulation 332 harmonic oscillator approximation in crystalline tropolone (HOA) 8, 253, 281, 393, 395 343–344 harmonic oscillators 208, 389, 502, crystalline vitamin C 336–338 504, 512 2-hydroxy-5-nitrobenzamide harmonic potential energy function 332 543 infrared spectroscopy 333 harmonic vibrational frequencies 354, oxalic acid dihydrate crystal, 516, 537 isotopic substitution effects Hartree–Fock (HF) 333–336 analytical approach 464 refinement and enhancement 332 approach 180 directional intermolecular calculations 227 interactions 328 exchange 83 historical and theoretical background methods 179, 358 329–332 theory 80, 254 quantitative reconstruction and Hartree-Fock/Kohn-Sham method interpretation 328 428 quantum effects 328 Hermite polynomials 512 hydrogen bonded system Herzberg–Teller (HT) contributions 9, anharmonic coupling 201 21, 503 acetic acid 211 Herzberg–Teller vibronic couplings formic acid 211–212 497, 523 limit situations 210–211 Hessian matrix 314, 429, 466, 467, 515, line shape 208–209 517 spectral density 203–206 hexanoic acid 367, 368 infra-red transitions 200 higher order excitations 579–580 linear response theory higher-order plasmon resonances electric dipole interaction 201 580 quantitative theory 202–203 Index 603

nuclear dynamics theories 200 336, 337, 355, 363–368, 371, 373, X-H stretching mode 200 427, 443, 459, 460, 473, 475, 476, hydrogen bond strength 218–220, 235, 484 236, 238, 241, 328, 334, 341, intermolecular translations 459, 460, 406 465, 467, 468, 472–475, 478–479, hydroquinone 294–296 485, 486 hyperpolarizability 308, 309, 311, intermolecular vibrational dynamics 313–318, 320 460 intra-and inter molecular vibrations i 430, 432, 433 IMDHO model 510, 513, 517–521, intramolecular hydrogen bonds 523 calculation of energies 220–223 implicit solvation model 358 Car–Parrinello molecular dynamics independent mode displaced harmonic simulations 232–234 oscillator (IMDHO) model definition 216 505, 506 donor and acceptor 215 INDO/SCI absorption spectra 578 double bond linking 216 inelastic neutron scattering (INS) 429, hydrogen bond strength 218–220 440, 460, 473 IR spectra, calculation of inelastic scattering 497, 500 harmonic approximation infrared (IR) 353 226–228 absorption 426 malonaldehyde and acetylacetone inorganic semiconductors 425 229–232 Integral Equation Formalism (IEF-PCM) static procedure 228–229 method 184, 257 NMR inter-and intra molecular vibrations, in Gauge Invariant Atomic Orbital charge transport (GIAO) method 234 electron-phonon coupling OH chemical shifts 235–236 local and non-local 434–436 resonance assisted hydrogen bonds in organic semiconductors (RAHB) 215 439–440 structural parameters, calculations of in various organic semiconductors 217 440–443 tautomerism electron-phonon interaction 2D approaches 223 436–439 potential energy and free energy Intermediate Neglect of Differential surfaces 223–226 Overlap Hamiltonian 576 intramolecular interaction 261–265 intermodal anharmonicities 369 intramolecular vibrations 429, 477 inter-modal anharmonicity 354 dynamics 460 intermolecular and intramolecular frequency sequences 478–479 vibrations 459, 461, 465–467, isotope shifts (IS) 474 471, 474, 476, 477, 479–481, 485, isotopomers 373, 374 487 isotropic hyperfine coupling constant intermolecular charge delocalization 11 425, 436, 437, 447 ith parent mode 174 intermolecular electronic coupling 425, 446, 448 j intermolecular interactions 126, 131, julolidinemalononitrile (JM) 183, 261–265, 328, 333, chromophore 518, 519 604 Index

k CH-stretching vibration 405 Kleinpeter–Koch approach 220 dimethylamine 412–413 Kohn–Sham (KS) Fermi-resonance coupling 396 density functional theory 180 ground state energy 392 determinant 64 harmonic oscillator approximation equation 465 393 Fock operator 48 HOH-bending mode 401 orbitals 463 intensities 408–417 Kramers–Kronig relations 510 intermolecular modes 406–408 Kramers–Kronig transformation 124, intermolecular modes in bimolecular 130 complexes 416–417 internal energy 390 l methyl torsion 414–415 l-alanine crystal 462, 476–478 Morse wavefunctions 410 large amplitude motions (LAMs) 10 NM approximation 390 l-ascorbic acid 337 off-diagonal contributions 390 lattice distortion energy 436, 441, 442 OH-stretching oscillators 393 lattice dynamics 459 OH-stretching vibrations 394 light–electron couplings 44, 50, 51, 57 symmetric and asymmetric linear-response (LR) TDDFT 62 fundamental transitions 395 linear response theory 177, 199–212 symmetric and asymmetric Liouville–von Neumann equation 49, transitions 412 51 2D LM Hamiltonian 394 lipid bilayer 157–160 water dimer 413–414 local electron-phonon coupling zeroth-order Hamiltonian 400 434–436, 438–444, 448 zeroth-order LM Hamiltonian 390 local (Holstein-type) electron-phonon low-temperature (LT) 128, 183, 263, coupling 435 285, 287, 294, 296, 442, 443, 471 local mode perturbation theory (LMPT) mode 406 m local modes 150–151, 389–417 magnetic-dipole transition moment local origin gauge (LORG) method (MDTM) 174 234–235 magnetic spectroscopy 2, 10–12, local oscillator (LO) 310 22–25 long chain FAs (LCFAs) 364 malic acid 369, 370 Lorentzian expansion 549 malonaldehydes 220, 229 Low barrier hydrogen bonds 216 enol 231 Löwdin orthogonalizaion 45 m-aminobenzonitrile 540 low-energy intramolecular vibrations Mannich bases 224, 234, 239 487 mass-weighted Cartesian coordinates lowest unoccupied molecular orbital 389, 467, 513, 515, 544 (LUMO) 52, 86, 89, 343, 434, matrix-isolation (MI) 183, 187, 255, 445, 566 269, 280–287, 290, 291, 293 low-frequency Raman spectra 431 matrix-isolation spectroscopy low frequency vibrations acetic acid 280 anharmonic oscillators (AO) 391 adoption of theory and basis set Birge–Sponer plot 393 282–283 Birge–Sponer type fit 392 conformational analysis CH-stretching frequencies 397–400 chlorobenzaldehyde 285–286 CH-stretching transitions 411 1,2-dichloroethane 283–285 Index 605

excitation light 289–290 molecular tailoring approach (MTA) vanillin 286–289 221, 222 identification of chemical species molecular weight (MW) 479 cytosine, rare tautomer of 290–291 molecule-Ag4 model 547 molecular complex/cluster molecule-cluster system 576 293–294 molecule-metallic cluster model 537, reversible isomerization, from 546 1,8-diaminonaphthalene molecule-silver clusters complexes 291–293 564 photoinduced transient species molecule weights, comparison 479 hydroquinone 294–296 Møller–Plesset MP2 method 369 lowest electronic excited triplet perturbation approach 81 state 296–297 second order perturbation (MP2) photolysis 282 358 wavenumber shifts of absorption Morse wavefunctions 405, 410 bands 281 Mulliken population analysis 54, 56, 57 matrix-isolation vibrational circular multichromophoric system 102 dichroism spectra (MI-VCD) multi-configurational methods 62, 517 183 multi-configurational SCF (MCSCF) medium chain FAs (MCFAs) 364 84 band assignments 368 multi-configuration self-consistent field NIR spectra 366 (MC SCF) model 179, 180 20-mer ethylene system 54 multi-dimensional harmonic PESs 513 meta-dicyanobenzenes 431 multiple charge transport models 436 methanol 37, 261–265, 279, 315, 316, multi-reference approaches 83 355, 357, 358 multivariate analytical (MVA) 369 methyl hexanoate 319 mode decomposition method n 465–468 natural bond orbital (NBO) analysis mode-mode couplings 353, 354 547 molecular crystals 427–430, 440, 2-(N-diethylamino-N-oxymethyl)-4,6- 459–462, 464, 465, 480 dichlorophenol 224 molecular dynamics (MD) 35, 59–70, near-infrared (NIR) spectroscopy 353, 94, 173, 184, 185, 217, 328, 330, 355 331, 345, 427 band assignments 357 molecular hyperpolarizability 308, basic molecules 355–363 313–318, 320 binary and ternary combination molecular mechanical calculation bands 375 (MMC) 273 butyl alcohols 361 molecular orbital (MOs) 550, 583 combination modes 353–383 energies 566 conformational isomerism 355, 357 interaction 537 cyclohexanol 363 molecular phonon modes 470 diluted methanol 356 adenine 475–476 fatty acids 364–368 anthracene 473–474 fundamentals 378–380 C60 471–473 intermolecular interactions and α-glycine and l-alanine 476–478 biomolecules 363–368 rigid-body approximation 471 miscellaneous applications 373–375 molecular structure refinement (MSR) overtone 353–383, 412–415 12, 16 phenol 363 606 Index

near-infrared (NIR) spectroscopy normal mode (NM) 9, 10, 17, 32, 105, (contd.) 151, 200, 226, 253, 256, 316, 354, rosmarinic acid 371 389, 428, 439, 461, 465–467, 478, single mode anharmonicity by solving 480 1D Schrödinger equation normal mode decomposition (NMD) 375–383 439 spectra-structure correlations 357 NTChem theoretical and analytical 368–373 computational methods 43 vibrational self-consistent filed K computer’s processing power 43 (VSCF) scheme 354 nuclear velocity perturbation theory 2-(N-ethyl-α-iminoethyl)-4-chloro-5- (NVPT) 173, 191 methylphenol 232, 233 nylon6, hydration of 160 Newton equations of motion 354 nylons 120 Newton’s law of motion 541 ATR-FUV spectra 137 Gaussian functions 139 NH2 group 539, 546, 549, 551, 553, 565, 567 hydrogen bonding 139 NH stretching modes 155, 380–382 intermolecular hydrogen bonding 141 NH2 wagging mode (ωNH2) 538 NIRS 353 N-methylacetamide (NMA) 136 π π N-isopropylacetamide 263 - *bands 140 π-π* transition 140, 141 nitroxides 35 𝜎-Rydberg transitions 140 N-methylacetamide (NMA) 122, 130, trintensity 137 136, 263 N-methyl-2-hydroxybenzylidene amine o (HBZA) 234 o-aminobenzonitrile 540 2-(N-methyliminomethyl)-4,6- o-dimethylaminomethylphenol (DMAP) dichlorophenol 232, 233 234 N,N-dimethylacetoamide (NdMAm) off-resonance energy 590 130, 255–261 O-H stretching modes 480 Noble metal nanoparticles 575 o-hydroxy aromatic aldehydes 222, nonadiabatic coupling (NAC) 50, 61, 235, 241 64–65 o-hydroxyarylaldehydes 220 nonadiabatic molecular dynamics o-hydroxyaryl Schiff bases 223, 224, simulation 61 232 non-annealed scPLA 485 o-hydroxy Schiff base 234 non-covalent interactions 100, 428, olefins 537, 538, 540, 546, 558–562, 460, 462–465, 470–481 567 nonlocal correlation density functionals oligoacenes 440–442 463 oligothiophenes 429, 440–443 non-local (Peierls-type) coupling 435 optical phonon modes 427, 461, 462, non-local electron-phonon coupling 470–481 434–436, 438–444, 448 orbital Zeeman (OZ) 11 non-local electron-phonon interaction organic crystals, LF vibrations 426 444, 446 organic electronic devices 425 non-resonant Raman scattering 498, organic light-emitting diodes (OLEDs) 501 425 non-vibrationally resonant anti-Stokes organic semiconductor crystals (OSCs) transition 315 425, 449 Index 607

charge transport properties 425, 426 polarity 311–313 organic semiconductors 425, 436–443 polarizable continuum models (PCMs) organic semiconductorsis 425 35, 121, 183, 184, 279, 518 organic solar cells 425 polaron binding energy 435, 436, 442 ortho-dicyanobenzenes 431 poly(d-lactic acid) (PDLA) 481, 484 oxalic acid dihydrate crystal 329, poly(l-lactic acid) (PLLA) 481, 484 333–336 polymer materials 160–163, 481–484 poly(methyl methacrylate) 318 p poly(N,N-dimethylacrylamide) p-aminobenzoic acid (PABA) (PNdMAm) 261 538–540, 549 poly(N-isopropylacrylamide) (PNiPAm) p-aminobenzoic acid methyl ester 262 (PABM) 549 polycrystalline TCNQ 431 p-aminobenzonitrile (PABN) poly(lactic acid) stereocomplex (scPLA) 538–540, 549 481–483 p-aminothiophenol 540, 554 polypeptides 153–167 para-dicyanobenzenes 431 portable batch system (PBS) 25 para-substituted anilines 556 post-DFT approaches 463 path integral molecular dynamics post-Hartree–Fock approaches 21 (PIMD) 329 post-molecular dynamics analysis 331 p-bromoaniline (PBA) 549 potential energy distribution (PED) p-chloroaniline (PCA) 549 466, 545 Peierls-type coupling 435 potential energy surface (PES) 5, 59, pentacene crystal 442 94, 147, 185, 217, 327, 330, 345, pentapeptide 153–157 428, 461, 502 perturbation-corrected VSCF potential of zero charge (PZC) 554 (PT2-VSCF) 354 powerful graphical user interface (GUI) perturbation theory 5, 62, 148, 152, 3 173, 186, 229, 354, 390, 516 p-π conjugated molecules 538, 540, (–)-1-phenylethanol 270 546 phonon-assisted charge transport 437, p-π conjugation effect 537, 560 438 P(Harm) procedure 229, 230 phonon modes 461, 487 projector augmented wave (PAW) atomic vibrations 459 method 123 center of mass 460 1-propanol 261, 357, 358 phonons, types 427 propionic acid 365, 366 photoisomerization 95, 96 propylene free radicals 547, 557 photolysis 282, 289, 293, 294, 411 propylene radical anion 557 picolinic acid N-oxide (PANO) 217, prototypical intermolecular interactions 234 459 π-bonded adsorption 546 p-substituted aniline derivatives 537, π-bonded configuration 546, 560 538 Placzek approximation 501 Pulay’s definition of internal coordinates Placzek polarizability theory 508 541 plasmon 575, 583 pyrol-ethylene systems 382 plasmon-like dipolar excited states 581 pyrrole-acetylene systems 382 p-methoxyaniline (PMOA) 549 pyrrole–pyridine complex 381, 382 p-methylaniline (PMA) 549 Python program VASP_RAMAN.PY p-nitroaniline (PNA) 549 428 608 Index

q spectral lineshape 93–95 QM/MM exciton model Hamiltonian spin-flip (SF) approach 83 105 state-averaged CASSCF quadrupolar plasmonic excited states (SA-CASSCF) approach 84 582, 590 symmetry-adapted-cluster quantum chemical approaches 439 configuration interaction quantum-chemical methods 12–14, (SAC-CI) method 82 329 tetracene and pentacene dimers quantum chemistry (QC) 88 electronic spectroscopy for methods 497, 499 absorption predictions 97–99 resonance raman spectra 517 algebraic diagrammatic quantum effects 225, 226, 328, 330, construction (ADC) 81 343 bacteriochlorophylls, in LH2 quantum mechanical (QM) simulations 102–107 353–383 charge transfer (CT) transitions quantum mechanical theory 176, 499 83 Quantum Monte Carlo techniques 223 chemical calculations 88–93 quartic centrifugal-distorsion complete active space SCF Hamiltonian 5 (CASSCF) 84 quartic force field approximation 369 configuration interaction singles quasistatic approximation 575 (CIS) 80 Coulombic and exchange r interactions 87 radiation absorption 353 Coulombic dipole interaction 86 Raman activity 19, 160, 503, 553 coupled cluster singles and doubles Raman effect 497 (CCSD) method 82 Raman frequency 561 coupling, excitation energies 104 Raman intensities 181, 497, 499, 537, density functional theory (DFT) 547, 548, 553, 568 82 C-NH2 stretching vibration 557 donor highest occupied molecular Raman intensity 172, 181, 431, 537, orbital (dHOMO) 86 548–549 dynamics simulations 105–107 Raman polarizability tensor 500–502, equation-of-motion coupled cluster 508, 521 (EOM-CC) approach 81 Raman scattering 305, 306, 316, excited state energies 103 497–517, 548 Hartree–Fock (HF) theory 80 (normal) Raman scattering (NRS) 587 isolated retinal 96–97 Raman spectra 555, 556 MD simulations, with QM/MM aniline 551, 553, 554 99–100 ethylene 562 Møller–Plesset (MP2) perturbation PABA 557 approach 81 PATP 555 multichromophoric systems 85 Raman spectroscopy 353, 440, 460, multiconfigurational SCF (MCSCF) 568 approaches 84 F2n-TCNQ crystals 430 multiexcitonic behaviors 88 by solid-state DFT 429 retinal in rhodopsin 95–102 techniques 95 rhodopsin variants 100 Raman transition 521 Slater determinant 87 R3c space-group symmetry 481 Index 609 replica-exchange molecular dynamics Ser-Ile-Val-Ser-Phe (SIVSF). SIVSF (REMD) method 154 153 resonance assisted hydrogen bonds SFG 304–307 (RAHB) 215 SFG phase measurement 310–311 resonance polarizability derivatives short chain FAs (SCFAs) 364 508–509 molecular structures 365 resonance Raman (RR) intensities 506 short-time approximation (STA) 497, time-dependent formulation 508 507, 518 resonance Raman (RR) scattering 498, silver clusters 539, 540, 546, 548, 554, 519, 522 555, 558, 559, 562, 564, 576 resonance Raman spectra 588, 591 silver nanoclusters 576 resonance ROA (RROA) 181 simplified approximation 511 restricted active space perturbation simulations of surface-enhanced ROA theory 517 (SERROA) 181 reverse osmosis (RO) 160 single and double excitation Rhodamine 6G (R6G) 518, 520 configuration interaction (SDCI) rhodopsin 79 577 variants 100 single excitations (SCI) 80, 83, 86, rigid-rotor harmonic-oscillator (RRHO) 577–579 approximation 5 site-directed labelling techniques 10 model 19 Slater determinants 80, 83, 84, 89, 90 root-mean-square (RMS) deviation 15 small-molecular crystals 464 root-mean-square mass-weighted small-shift approximation 506, 511 atomic displacement snap shot 149 (RMSMWAD) 470 solid-state DFT (DFT) 427, 434, 459, rosmarinic acid (RA) 370, 373 461, 481, 486 band assignments 372 solute model of density (SMD) 547 NIRS 371 solvation 265–269 rotational spectroscopy 4–5, 14–16 sorbic acid 367, 368 RR excitation profile (RREP) 521 spectral density 202–206 spectral lineshape 93 s spectral simulations, flexible molecules salicylaldehyde 218, 220, 221, 237 Ar matrix 256 saturated hexanoic sorbic acid 367 conformational diversity Savin formula 506, 507 electronic circular dichroism scaled quantum mechanicals force field 272–275 (SQMFF)method 546 vibrational circular dichroism scPLA, effect of crystallinity 485 (VCD) spectroscopy 269–272 second-order Møller-Plesset (MP2) level vibrational spectrum, solvation in 516 265–269 second-order perturbation corrected electronic circular dichroic (ECD) scheme (PT2-VSCF) 369 spectra 254 self-consistent field (SCF) HF solution intra-and inter-molecular interaction 80 254 self-consistent reaction field (SCRF) intramolecular and intermolecular 257, 358 interactions 261–265 self-localization 437, 438 scaling factor 257 semiempirical electronic structure in solution phase 257 method 576 ternary amide compound 254 610 Index

spectral simulations, flexible molecules nonlinear optical techniques 304 (contd.) surface sum-frequency generation 537 vibrational circular dichroism (VCD) surface vibrational optical spectroscopic 254 techniques 537 vibrational spectra 254 surface vibrational spectroscopy 568 wavenumber linear scaling method symmetry-adapted-cluster 257 configuration interaction spectra-structure correlations 360 (SAC-CI) method 82 sphingomyelin (SM) bilayers 149, symmetry-adapted perturbation theory 157–160 (SAPT) 462 spin-flip (SF) approach 70, 83 symmetry-conservation law 481 spin-forbidden circular dichroism 177–179 t spin-forbidden processes 70, 71 Tamm–Dancoff approximation (TDA) spin orbit coupling (SOC) operators 83 11, 70 tautomerism S-propylene oxide (S-PO) 189 potential energy and free energy state-averaged CASSCF (SA-CASSCF) surfaces 223–226 62 2D approaches 223 Stokes Raman scattering 305, 498 TCNQ, charge transfer directions 445 Stokes scattering 498, 502, 586 template molecule (TM) approach 31 sum-over-states (SOS) 499, 501, 585 terahertz (THz) spectroscopy 459 supermolecular approach 183 terminal olefin 537–539, 546, 558–562 super-sonic jet technique 279 tetrahedral Ag20 cluster 578 surface adsorption interaction 546 tetramethylsilane (TMS) 235 surface enhanced infrared spectroscopy thermally populated low-frequency (LF) 539, 565 vibrations 426 surface enhanced Raman scattering thin-film electronics 425 (SERS) 537, 575 THz spectroscopy 459–487 density functional theoretical time correlation function (TCF) 173, calculations 546 176, 191 modeling molecules time-dependent complete active space aniline 549–554 self-consistent field benzyl radicals anion 557–558 (TDCASSCF) theory 48 broad bands 565–567 time-dependent density functional chemical enhancement effect theory (TDDFT) 179, 508, 516, 562–565 517, 575 para-substituted anilines time dependent Hartree–Fock (TDHF) 554–557 46, 48 terminal olefin 558–562 time-dependent perturbation theory normal mode analysis 541 497, 499 p-π conjugated molecules 538 time-dependent potentials 226 Raman intensity 548–549 time independent (TI) sum-over-states voltage effects and chemical approach 10 mechanism 591 time-resolved fluorescence 95 wagging vibrational Raman spectra tip enhanced Raman scattering (TERS) 538–540 576, 585 surface spectroscopy torsion, of methyl group 414–415 label-free method 303 total density of states (TDOS) 128 Index 611 trajectory surface hopping molecular vibrational circular dichroism (VCD) dynamics simulation spectroscopy 269–272 computational details 66 vibrational configuration interaction conical intersection (VCI) method 355 lifetime and transition rate 61 vibrational coupled-cluster (VCC) path and role of 60–61 method 355 effects of environment 69 vibrational energy 6, 69, 153, 470, electronic structure methods 62–63 480 NAMD simulation 61 vibrational frequency 547 photodynamics of coumarin 65–66 in crystals 433 results and discussion 66–69 vibrational Hamiltonian 389, 391, 418, spin-forbidden processes 70 507, 515 S0/S1 crossing 69–70 vibrational optical activity 180–181 theoretical method vibrational perturbation theory (VPT) LR-TDDFT method 63–64 147, 186, 229, 354, 358 nonadiabatic coupling 64–65 vibrational quasi-degenerate TSH approach 63 perturbation theory 151–152 transfer (hopping) rate 438 vibrational resonance Raman spectra of transform theory 509–511 molecules transition intensity 354 quantum chemistry methods transition quadrupole moments 581, 515–517 582 applications 518 transmission electron microscopy double harmonic approximation (TEM) 440 501–503 trans-porphycene 523, 524 electronic excited states in 1,3,5-triacetyl-2,4,6-trihydroxybenzene resonance 521–523 220, 222, 223 Franck–Condon overlap integrals Tully’s fewest switch surface hopping 511–515 approach Franck–Condon vibronic couplings conical intersection, crossing point 518–521 61 Herzberg–Teller vibronic couplings electronic structure methods 63 523 tunnelling effect 203 intensities 503–506 two-dimensional correlation analysis resonance polarizability derivatives (2D-COS) 358 508–509 2D electronic spectroscopy 100 short-time approximation 518 two-electron one-center integrals 576 sum-over-state formulation 499–501 u time-dependent formulation urea, molecular structures 461 506–508 transform theory and simplified v approximation 509–511 vanillin 286–289 time-dependent perturbation theory vertical gradient (VG) model 10, 517 497 vertical Hessian (VH) model 10, 517 vibrational second-order perturbation vibrational absorption spectra (VA) theory (VPT2) 229 173 vibrational self-consistent field (VSCF) vibrational analysis 122, 281, 282, 284, 148, 228, 354, 369 297, 330, 370 vibrational spectral analysis 279, 540 612 Index

vibrational spectroscopy 16–19, 254, wavenumber linear scaling method 357, 373, 427, 428 257 techniques 538 weight averaged anharmonic vibrational vibrational sum-frequency generation calculations spectroscopy cluster and local modes 150–151 experimental studies 304–307 computational procedure 153 SFG phase measurement 310–311 conventional vibrational calculations vibronic Bohr frequencies 503 147 vibronic spectroscopy 8–10, GENESIS 148 19–22 IR spectroscopy 147 vibronic theory 510, 511 MD simulations 148 Vienna ab initio simulation package nylon6, hydration of 160–163 (VASP) 122–123 pentapeptide, SIVSF 153–157 vinylacetic acid 365–367, 376 second-order vibrational perturbation virtual multifrequency spectrometer theory 148 (VMS) sphingomyelin (SM) bilayers computational and experimental 157–160 spectroscopic techniques 3 vibrational quasi-degenerate glycine case study 26–28 perturbation theory 151–152 graphical user interface (GUI) 3 vibrational self-consistent field physical-chemical features 3 (VSCF) 148 rotational spectroscopy 14–16 weight average method 149–150 theoretical background magnetic spectroscopy 10–12, x 22–25 X-ray diffraction 171, 481 quantum-chemical methods X-ray photoelectron spectroscopy (XPS) 12–14 443 rotational spectroscopy 4–5 vibrational spectra 5–8 z vibrational spectroscopy 16–19 zero-differential overlap approximation vibronic spectroscopy 8–10 576 vibronic spectroscopy, methyloxirane zero-point-energy-correction (ZPE) case study 28–30 180 in vitro and in silico experiments 3 zeroth-order expression 394 zeroth-order Hamiltonian 84, 397, w 400, 401, 410 Wannier functions 335, 440 zeroth-order regular approximation Wannier localization function 331, (ZORA) 577 332 zwitterionic 1,8-bis(dimethylamino)- water dimer 413–414 4,5-dihydroxynaphthalene 227