Improving Rydberg Excitations within Time-Dependent Density Functional Theory with Generalized Gradient Approximations: The Exchange-Enhancement-for-Large-Gradient Scheme
- Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, United States
Time-dependent density functional theory (TDDFT) with conventional local and hybrid functionals such as the local and hybrid generalized gradient approximations (GGA) seriously underestimates the excitation energies of Rydberg states, which limits its usefulness for applications such as spectroscopy and photochemistry. We present here a scheme that modifies the exchange-enhancement factor to improve GGA functionals for Rydberg excitations within the TDDFT framework while retaining their accuracy for valence excitations and for the thermochemical energetics calculated by ground-state density functional theory. The scheme is applied to a popular hybrid GGA functional and tested on data sets of valence and Rydberg excitations and atomization energies, and the results are encouraging. The scheme is simple and flexible. It can be used to correct existing functionals, and it can also be used as a strategy for the development of new functionals.
- Research Organization:
- Univ. of Minnesota, Minneapolis, MN (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Grant/Contract Number:
- SC0008666
- OSTI ID:
- 1252036
- Alternate ID(s):
- OSTI ID: 1455126
- Journal Information:
- Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Vol. 11 Journal Issue: 7; ISSN 1549-9618
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
Web of Science
MN15: A Kohn–Sham global-hybrid exchange–correlation density functional with broad accuracy for multi-reference and single-reference systems and noncovalent interactions
|
journal | January 2016 |
Perspective: Kohn-Sham density functional theory descending a staircase
|
journal | October 2016 |
The ring-opening channel and the influence of Rydberg states on the excited state dynamics of furan and its derivatives
|
journal | August 2018 |
Similar Records
A New, Self-Contained Asymptotic Correction Scheme To Exchange-Correlation Potentials For Time-Dependent Density Functional Theory
Density Functionals with Broad Applicability in Chemistry