Revised M11 Exchange-Correlation Functional for Electronic
Excitation Energies and Ground-State Properties
Version 2 2019-03-15, 12:35
Version 1 2019-03-14, 19:34
Posted on 2019-03-15 - 12:35
The
ability of Kohn–Sham density functional theory (KS-DFT)
to accurately predict various types of electronic excitation energies
with (necessarily approximate) exchange-correlation functionals faces
several challenges. Chief among these is that valence excitations
are usually inherently multiconfigurational and therefore best treated
by functionals with local exchange, whereas Rydberg and charge-transfer
excitations are often better treated with nonlocal exchange. The question
arises regarding whether one can optimize a functional such that all
three kinds of excitations (valence, Rydberg, and charge transfer,
including long-range charge transfer) are treated in a balanced and
accurate way. The goal of the present work is to try to answer that
question and then to optimize a functional with the best possible
balanced behavior. Of the variety of functional types available, we
choose to use a range-separated hybrid meta functional for the following
reasons: (i) Range separation allows the percentage of Hartree–Fock
(HF) exchange to change with interelectronic separation, and therefore,
one can have 100% HF exchange at large interelectronic separations,
which gives good performance for long-range charge-transfer excitations,
while the range separation allows one to simultaneously have smaller
values of HF exchange at small and intermediate interelectronic separations,
giving good performance for valence and Rydberg excitations. (ii)
Meta functionals allow one to obtain better accuracy with high HF
exchange than is possible with functionals whose local part depends
only on spin densities and their gradients. This work starts with
the range-separated hybrid meta functional M11 and reoptimizes it
(with strong smoothness restraints) against electronic excitation
energies and ground-state properties to obtain a new functional called
revM11 that gives good performance for all three types of electronic
excitations and at the same time gives very good predictions across
the board for ground-state properties.
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Verma, Pragya; Wang, Ying; Ghosh, Soumen; He, Xiao; Truhlar, Donald G. (2019). Revised M11 Exchange-Correlation Functional for Electronic
Excitation Energies and Ground-State Properties. ACS Publications. Collection. https://doi.org/10.1021/acs.jpca.8b11499
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AUTHORS (5)
PV
Pragya Verma
YW
Ying Wang
SG
Soumen Ghosh
XH
Xiao He
DT
Donald G. Truhlar