Header

UZH-Logo

Maintenance Infos

Efficient calculation of (resonance) Raman spectra and excitation profiles with real-time propagation


Mattiat, Johann; Luber, Sandra (2018). Efficient calculation of (resonance) Raman spectra and excitation profiles with real-time propagation. Journal of Chemical Physics, 149(17):174108.

Abstract

We investigate approaches for the calculation of (resonance) Raman spectra in a real-time time-dependent density functional theory (RT-TDDFT) framework. Several short time approximations to the Kramers, Heisenberg, and Dirac polarizability tensor are examined with regard to the calculation of resonance Raman spectra: One relies on a Placzek type expansion of the electronic polarizability and the other one relies on the excited state gradient method. The first one is shown to be in agreement with an approach based on perturbation theory in the case of a weak δ-pulse perturbation. The latter is newly applied in a real time propagation framework, enabled by the use of Padé approximants to the Fourier transform which allow for a sufficient resolution in the frequency domain. An analysis of the performance of Padé approximants is given. All approaches were found to be in good agreement for uracil and R-methyloxirane. Moreover it is shown how RT-TDDFT can be used to calculate Raman excitation profiles efficiently.

Abstract

We investigate approaches for the calculation of (resonance) Raman spectra in a real-time time-dependent density functional theory (RT-TDDFT) framework. Several short time approximations to the Kramers, Heisenberg, and Dirac polarizability tensor are examined with regard to the calculation of resonance Raman spectra: One relies on a Placzek type expansion of the electronic polarizability and the other one relies on the excited state gradient method. The first one is shown to be in agreement with an approach based on perturbation theory in the case of a weak δ-pulse perturbation. The latter is newly applied in a real time propagation framework, enabled by the use of Padé approximants to the Fourier transform which allow for a sufficient resolution in the frequency domain. An analysis of the performance of Padé approximants is given. All approaches were found to be in good agreement for uracil and R-methyloxirane. Moreover it is shown how RT-TDDFT can be used to calculate Raman excitation profiles efficiently.

Statistics

Citations

Dimensions.ai Metrics
4 citations in Web of Science®
4 citations in Scopus®
Google Scholar™

Altmetrics

Downloads

17 downloads since deposited on 14 Feb 2019
16 downloads since 12 months
Detailed statistics

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:7 November 2018
Deposited On:14 Feb 2019 14:31
Last Modified:05 Nov 2019 01:00
Publisher:American Institute of Physics
ISSN:0021-9606
OA Status:Green
Publisher DOI:https://doi.org/10.1063/1.5051250
Project Information:
  • : FunderSwiss National Foundation
  • : Grant IDPP00P2 170667
  • : Project Title
  • : FunderUniversity Research Priority Program
  • : Grant IDLightChEC
  • : Project Title

Download

Green Open Access

Download PDF  'Efficient calculation of (resonance) Raman spectra and excitation profiles with real-time propagation'.
Preview
Content: Published Version
Filetype: PDF
Size: 1MB
View at publisher