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Electronic circular dichroism from real-time propagation in state space

Monti, M
•
Stener, M
•
Coccia, E
2023
  • journal article

Periodico
THE JOURNAL OF CHEMICAL PHYSICS
Abstract
In this paper, we propose to compute the electronic circular dichroism (ECD) spectra of chiral molecules using a real-time propagation of the time-dependent Schrodinger equation (TDSE) in the space of electronic field-free eigenstates, by coupling TDSE with a given treatment of the electronic structure of the target. The time-dependent induced magnetic moment is used to compute the ECD spectrum from an explicit electric perturbation. The full matrix representing the transition magnetic moment in the space of electronic states is generated from that among pairs of molecular orbitals. In the present work, we show the ECD spectra of methyloxirane, of several conformers of L-alanine, and of the lambda-Co(acac)(3) complex, computed from a singly excited ansatz of time-dependent density functional theory eigenstates. The time-domain ECD spectra properly reproduce the frequency-domain ones obtained in the linear-response regime and quantitatively agree with the available experimental data. Moreover, the time-domain approach to ECD allows us to naturally go beyond the ground-state rotationally averaged ECD spectrum, which is the standard outcome of the linear-response theory, e.g., by computing the ECD spectra from electronic excited states.
DOI
10.1063/5.0136392
WOS
WOS:000937824600009
Archivio
https://hdl.handle.net/11368/3046082
info:eu-repo/semantics/altIdentifier/scopus/2-s2.0-85148890882
https://pubs.aip.org/aip/jcp/article/158/8/084102/2868792/Electronic-circular-dichroism-from-real-time
Diritti
open access
license:copyright editore
license:copyright editore
license:digital rights management non definito
license uri:iris.pri02
license uri:iris.pri02
license uri:iris.pri00
FVG url
https://arts.units.it/bitstream/11368/3046082/1/jcp158_084102.pdf
Soggetti
  • Circular Dichroism

  • Time Dependent Densit...

  • Real Time Propagation...

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