10.1021/acs.jctc.7b00666.s001
Feizhi Ding
Feizhi
Ding
Takashi Tsuchiya
Takashi
Tsuchiya
Frederick R. Manby
Frederick R.
Manby
Thomas F. Miller
Thomas F.
Miller
Linear-Response Time-Dependent Embedded Mean-Field
Theory
American Chemical Society
2017
transition properties
mean-field
TD
XAS
EMFT
sulfur K-edge X-ray absorption spectroscopy
TD-EMFT
2017-08-07 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Linear-Response_Time-Dependent_Embedded_Mean-Field_Theory/5357998
We present a time-dependent (TD)
linear-response description of
excited electronic states within the framework of embedded mean-field
theory (EMFT). TD-EMFT allows for subsystems to be described at different
mean-field levels of theory, enabling straightforward treatment of
excited states and transition properties. We provide benchmark demonstrations
of TD-EMFT for both local and nonlocal excitations in organic molecules,
as well as applications to chlorophyll a, solvatochromic shifts of
a dye in solution, and sulfur K-edge X-ray absorption spectroscopy
(XAS). It is found that mixed-basis implementations of TD-EMFT lead
to substantial errors in terms of transition properties; however,
as previously found for ground-state EMFT, these errors are largely
eliminated with the use of Fock-matrix corrections. These results
indicate that TD-EMFT is a promising method for the efficient, multilevel
description of excited-state electronic structure and dynamics in
complex systems.