Franck–Condon Models for Simulating the Band Shape of Electronic Absorption Spectra

Li, Shaohong L.; Truhlar, Donald G.

doi:10.1021/acs.jctc.7b00325

Title: Franck–Condon Models for Simulating the Band Shape of Electronic Absorption Spectra

Journal Article · Wed May 10 00:00:00 EDT 2017 · Journal of Chemical Theory and Computation

DOI:https://doi.org/10.1021/acs.jctc.7b00325· OSTI ID:1480133

Li, Shaohong L. ^[1];

^[1]

Univ. of Minnesota, Minneapolis, MN (United States)

Band shape is an essential ingredient in the simulation of electronic absorption spectra. The excitation of multiple series of vibrational levels during an electronic excitation is a main contributor to band shapes. Here we present two simple models based on the Franck–Condon displaced-harmonic-oscillator model. The models are both derived from the time-dependent formulation of electronic spectroscopy. They assume that the transition dipoles do not depend on geometry and that the potential energy surfaces are locally quadratic; one model is second order in time and is called LQ2, and the other is third order in time and is called LQ3. These models are suitable for simulating the unresolved vibronic band shapes of electronic spectra that involve many vibrational modes. The models are straightforward and can be easily applied to simulate absorption spectra that are composed of many electronic transitions. As compared to carrying out molecular dynamics simulations, they require relatively few electronic structure calculations, and the additional cost for constructing the spectra is negligible. Therefore, the models are suitable for simulating the spectra of complex systems such as transition-metal complexes.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0008666; AC02-05CH11231

OSTI ID:: 1480133

Journal Information:: Journal of Chemical Theory and Computation, Vol. 13, Issue 6; ISSN 1549-9618

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 22 works

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Title: Franck–Condon Models for Simulating the Band Shape of Electronic Absorption Spectra

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