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Time Domain Simulation of (Resonance) Raman Spectra of Liquids in the Short Time Approximation


Mattiat, Johann; Luber, Sandra (2021). Time Domain Simulation of (Resonance) Raman Spectra of Liquids in the Short Time Approximation. Journal of Chemical Theory and Computation, 17(1):344-356.

Abstract

Real-time time-dependent density functional theory (RT-TDDFT) and ab initio molecular dynamics (AIMD) are combined to calculate non-resonant and resonant Raman scattering cross sections of periodic systems, allowing for an explicit quantum mechanical description of condensed phase systems and environmental effects. It is shown that this approach to Raman spectroscopy corresponds to a short time approximation of Heller's time-dependent formalism for the description of Raman scattering. Two ways to calculate the frequency-dependent polarizability in a periodic system are presented: (1) via the modern theory of polarization (Berry phase) and (2) via the velocity representation. Both approaches are found to be equivalent for a system of liquid (S)-methyloxirane with the computational settings used. Resulting non-resonance and resonance Raman spectra from the dynamic AIMD/RT-TDDFT approach are compared to the spectra of one gas phase molecule in the harmonic approximation highlighting finite temperature and solvation effects. Using RT-TDDFT to calculate the full frequency-dependent Placzek-type polarizability within one set of simulations covers the non-resonance, near-resonance, and on-resonance regimes on equal footing, thus allowing the calculation of full Raman excitation profiles.

Abstract

Real-time time-dependent density functional theory (RT-TDDFT) and ab initio molecular dynamics (AIMD) are combined to calculate non-resonant and resonant Raman scattering cross sections of periodic systems, allowing for an explicit quantum mechanical description of condensed phase systems and environmental effects. It is shown that this approach to Raman spectroscopy corresponds to a short time approximation of Heller's time-dependent formalism for the description of Raman scattering. Two ways to calculate the frequency-dependent polarizability in a periodic system are presented: (1) via the modern theory of polarization (Berry phase) and (2) via the velocity representation. Both approaches are found to be equivalent for a system of liquid (S)-methyloxirane with the computational settings used. Resulting non-resonance and resonance Raman spectra from the dynamic AIMD/RT-TDDFT approach are compared to the spectra of one gas phase molecule in the harmonic approximation highlighting finite temperature and solvation effects. Using RT-TDDFT to calculate the full frequency-dependent Placzek-type polarizability within one set of simulations covers the non-resonance, near-resonance, and on-resonance regimes on equal footing, thus allowing the calculation of full Raman excitation profiles.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
08 Research Priority Programs > Solar Light to Chemical Energy Conversion
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Computer Science Applications
Physical Sciences > Physical and Theoretical Chemistry
Uncontrolled Keywords:Physical and Theoretical Chemistry, Computer Science Applications
Language:English
Date:12 January 2021
Deposited On:11 Oct 2021 14:20
Last Modified:26 Mar 2024 02:39
Publisher:American Chemical Society (ACS)
ISSN:1549-9618
OA Status:Green
Publisher DOI:https://doi.org/10.1021/acs.jctc.0c00755
Project Information:
  • : FunderSNSF
  • : Grant IDPP00P2_170667
  • : Project TitleIn Silico Investigation and Design of Bio-inspired Catalysts for Water Splitting
  • Content: Accepted Version