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Vibrational (resonance) Raman optical activity with real time time dependent density functional theory


Mattiat, Johann; Luber, Sandra (2019). Vibrational (resonance) Raman optical activity with real time time dependent density functional theory. Journal of Chemical Physics, 151(23):234110.

Abstract

We present a novel approach for the calculation of vibrational (resonance) Raman optical activity (ROA) spectra based on real time propagation. The ROA linear electronic response tensors are formulated in a propagator formalism in order to treat linear response (LR-) and real time time dependent density functional theory (RT-TDDFT) on equal footing. The length, mixed, and velocity representations of these tensors are discussed with respect to the potential origin dependence of the ROA invariants in the calculations. The propagator formalism allows a straight forward extension of the optical LR tensors in a mixed or velocity representation to a coupling with nonlocal potentials, where an extra term appears in the definition of the momentum operator, in order to maintain the gauge invariance. Using RT-TDDFT paves the way for an innovative, efficient calculation of both on- and off-resonance ROA spectra. Exemplary results are given for the off-resonance and (pre-)resonance spectra of (R)-methyloxirane, considering the resonance effects due to one or more electronically excited states. Moreover, the developed real time propagation approach allows us to obtain entire excitation profiles in a computationally efficient way.

Abstract

We present a novel approach for the calculation of vibrational (resonance) Raman optical activity (ROA) spectra based on real time propagation. The ROA linear electronic response tensors are formulated in a propagator formalism in order to treat linear response (LR-) and real time time dependent density functional theory (RT-TDDFT) on equal footing. The length, mixed, and velocity representations of these tensors are discussed with respect to the potential origin dependence of the ROA invariants in the calculations. The propagator formalism allows a straight forward extension of the optical LR tensors in a mixed or velocity representation to a coupling with nonlocal potentials, where an extra term appears in the definition of the momentum operator, in order to maintain the gauge invariance. Using RT-TDDFT paves the way for an innovative, efficient calculation of both on- and off-resonance ROA spectra. Exemplary results are given for the off-resonance and (pre-)resonance spectra of (R)-methyloxirane, considering the resonance effects due to one or more electronically excited states. Moreover, the developed real time propagation approach allows us to obtain entire excitation profiles in a computationally efficient way.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Uncontrolled Keywords:Physical and Theoretical Chemistry, General Physics and Astronomy
Language:English
Date:21 December 2019
Deposited On:07 Feb 2020 13:53
Last Modified:08 Feb 2020 08:38
Publisher:American Institute of Physics
ISSN:0021-9606
Additional Information:Copyright 2020 AIP Publishing. This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. The following article appeared in the Journal of Chemical Physics and may be found at 10.1063/1.5132294
OA Status:Closed
Publisher DOI:https://doi.org/10.1063/1.5132294
Project Information:
  • : FunderSNSF
  • : Grant IDPP00P2_170667
  • : Project TitleIn Silico Investigation and Design of Bio-inspired Catalysts for Water Splitting
  • : FunderUniversity Research Priority Program
  • : Grant ID
  • : Project TitleLightChEC)

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Embargo till: 2020-12-19