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Title: Origin invariance in vibrational resonance Raman optical activity

Abstract

A theoretical investigation on the origin dependence of the vibronic polarizabilities, isotropic and anisotropic rotational invariants, and scattering cross sections in Resonance Raman Optical Activity (RROA) spectroscopy is presented. Expressions showing the origin dependence of these polarizabilities were written in the resonance regime using the Franck-Condon (FC) and Herzberg-Teller (HT) approximations for the electronic transition moments. Differently from the far-from-resonance scattering regime, where the origin dependent terms cancel out when the rotational invariants are calculated, RROA spectrum can exhibit some origin dependence even for eigenfunctions of the electronic Hamiltonian. At the FC level, the RROA spectrum is completely origin invariant if the polarizabilities are calculated using a single excited state or for a set of degenerate states. Otherwise, some origin effects can be observed in the spectrum. At the HT level, RROA spectrum is origin dependent even when the polarizabilities are evaluated from a single excited state but the origin effect is expected to be small in this case. Numerical calculations performed for (S)-methyloxirane, (2R,3R)-dimethyloxirane, and (R)-4-F-2-azetidinone at both FC and HT levels using the velocity representation of the electric dipole and quadrupole transition moments confirm the predictions of the theory and show the extent of origin effects and themore » effectiveness of suggested ways to remove them.« less

Authors:
;  [1];  [2];  [3]
  1. Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Moruzzi 3, 56124 Pisa (Italy)
  2. Department of Chemistry, University of Washington, Seattle, Washington 98195 (United States)
  3. Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126 Pisa (Italy)
Publication Date:
OSTI Identifier:
22415730
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 17; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ANISOTROPY; CROSS SECTIONS; EIGENFUNCTIONS; ELECTRIC DIPOLES; EPOXIDES; EXCITED STATES; FRANCK-CONDON PRINCIPLE; HAMILTONIANS; OPTICAL ACTIVITY; ORGANIC NITROGEN COMPOUNDS; POLARIZABILITY; RAMAN SPECTROSCOPY; RESCATTERING; RESONANCE; RESONANCE SCATTERING; VELOCITY

Citation Formats

Vidal, Luciano N., E-mail: lnvidal@utfpr.edu.br, Cappelli, Chiara, E-mail: chiara.cappelli@unipi.it, Egidi, Franco, and Barone, Vincenzo. Origin invariance in vibrational resonance Raman optical activity. United States: N. p., 2015. Web. doi:10.1063/1.4918935.
Vidal, Luciano N., E-mail: lnvidal@utfpr.edu.br, Cappelli, Chiara, E-mail: chiara.cappelli@unipi.it, Egidi, Franco, & Barone, Vincenzo. Origin invariance in vibrational resonance Raman optical activity. United States. doi:10.1063/1.4918935.
Vidal, Luciano N., E-mail: lnvidal@utfpr.edu.br, Cappelli, Chiara, E-mail: chiara.cappelli@unipi.it, Egidi, Franco, and Barone, Vincenzo. Thu . "Origin invariance in vibrational resonance Raman optical activity". United States. doi:10.1063/1.4918935.
@article{osti_22415730,
title = {Origin invariance in vibrational resonance Raman optical activity},
author = {Vidal, Luciano N., E-mail: lnvidal@utfpr.edu.br and Cappelli, Chiara, E-mail: chiara.cappelli@unipi.it and Egidi, Franco and Barone, Vincenzo},
abstractNote = {A theoretical investigation on the origin dependence of the vibronic polarizabilities, isotropic and anisotropic rotational invariants, and scattering cross sections in Resonance Raman Optical Activity (RROA) spectroscopy is presented. Expressions showing the origin dependence of these polarizabilities were written in the resonance regime using the Franck-Condon (FC) and Herzberg-Teller (HT) approximations for the electronic transition moments. Differently from the far-from-resonance scattering regime, where the origin dependent terms cancel out when the rotational invariants are calculated, RROA spectrum can exhibit some origin dependence even for eigenfunctions of the electronic Hamiltonian. At the FC level, the RROA spectrum is completely origin invariant if the polarizabilities are calculated using a single excited state or for a set of degenerate states. Otherwise, some origin effects can be observed in the spectrum. At the HT level, RROA spectrum is origin dependent even when the polarizabilities are evaluated from a single excited state but the origin effect is expected to be small in this case. Numerical calculations performed for (S)-methyloxirane, (2R,3R)-dimethyloxirane, and (R)-4-F-2-azetidinone at both FC and HT levels using the velocity representation of the electric dipole and quadrupole transition moments confirm the predictions of the theory and show the extent of origin effects and the effectiveness of suggested ways to remove them.},
doi = {10.1063/1.4918935},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 17,
volume = 142,
place = {United States},
year = {2015},
month = {5}
}