Improving Rydberg Excitations within Time-Dependent Density Functional Theory with Generalized Gradient Approximations: The Exchange-Enhancement-for-Large-Gradient Scheme

Li, Shaohong L.; Truhlar, Donald G.

doi:10.1021/acs.jctc.5b00369

Title: Improving Rydberg Excitations within Time-Dependent Density Functional Theory with Generalized Gradient Approximations: The Exchange-Enhancement-for-Large-Gradient Scheme

Abstract

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.

Authors:

Li, Shaohong L. ^[1]; Truhlar, Donald G. ^[1]

Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, United States

Publication Date:: Wed Jun 17 00:00:00 EDT 2015

Research Org.:: Univ. of Minnesota, Minneapolis, MN (United States)

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

OSTI Identifier:: 1252036

Alternate Identifier(s):: OSTI ID: 1455126

Grant/Contract Number:: SC0008666

Resource Type:: Published Article

Journal Name:: Journal of Chemical Theory and Computation

Additional Journal Information:: Journal Name: Journal of Chemical Theory and Computation Journal Volume: 11 Journal Issue: 7; Journal ID: ISSN 1549-9618

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Li, Shaohong L., and Truhlar, Donald G. Improving Rydberg Excitations within Time-Dependent Density Functional Theory with Generalized Gradient Approximations: The Exchange-Enhancement-for-Large-Gradient Scheme.  United States: N. p., 2015. 
Web.  doi:10.1021/acs.jctc.5b00369.

Copy to clipboard


                    Li, Shaohong L., & Truhlar, Donald G. Improving Rydberg Excitations within Time-Dependent Density Functional Theory with Generalized Gradient Approximations: The Exchange-Enhancement-for-Large-Gradient Scheme.  United States.  https://doi.org/10.1021/acs.jctc.5b00369

Copy to clipboard


                    Li, Shaohong L., and Truhlar, Donald G. Wed .  
"Improving Rydberg Excitations within Time-Dependent Density Functional Theory with Generalized Gradient Approximations: The Exchange-Enhancement-for-Large-Gradient Scheme".  United States.  https://doi.org/10.1021/acs.jctc.5b00369.

Copy to clipboard


                    
@article{osti_1252036,

  title        = {Improving Rydberg Excitations within Time-Dependent Density Functional Theory with Generalized Gradient Approximations: The Exchange-Enhancement-for-Large-Gradient Scheme},

  author       = {Li, Shaohong L. and Truhlar, Donald G.},

  abstractNote = {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.},

  doi          = {10.1021/acs.jctc.5b00369},

  journal      = {Journal of Chemical Theory and Computation},

  number       = 7,

  volume       = 11,

  place        = {United States},

  year         = {Wed Jun 17 00:00:00 EDT 2015},

  month        = {Wed Jun 17 00:00:00 EDT 2015}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Publisher's Version of Record
https://doi.org/10.1021/acs.jctc.5b00369

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 26 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referencing / citing this record:

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

Yu, Haoyu S.; He, Xiao; Li, Shaohong L.
Chemical Science, Vol. 7, Issue 8
DOI: 10.1039/c6sc00705h

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

Yu, Haoyu S.; He, Xiao; Li, Shaohong L.
Chemical Science, Vol. 7, Issue 8
DOI: 10.1039/c6sc00705h

Perspective: Kohn-Sham density functional theory descending a staircase
journal, October 2016

Yu, Haoyu S.; Li, Shaohong L.; Truhlar, Donald G.
The Journal of Chemical Physics, Vol. 145, Issue 13
DOI: 10.1063/1.4963168

The ring-opening channel and the influence of Rydberg states on the excited state dynamics of furan and its derivatives
journal, August 2018

Schalk, O.; Geng, T.; Hansson, T.
The Journal of Chemical Physics, Vol. 149, Issue 8
DOI: 10.1063/1.5024655

Similar Records in DOE PAGES and OSTI.GOV collections:

Testing time-dependent density functional theory with depopulated molecular orbitals for predicting electronic excitation energies of valence, Rydberg, and charge-transfer states and potential energies near a conical intersection

Journal Article Li, Shaohong L. ; Truhlar, Donald G., E-mail: truhlar@umn.edu - Journal of Chemical Physics

Kohn-Sham (KS) time-dependent density functional theory (TDDFT) with most exchange-correlation functionals is well known to systematically underestimate the excitation energies of Rydberg and charge-transfer excited states of atomic and molecular systems. To improve the description of Rydberg states within the KS TDDFT framework, Gaiduk et al. [Phys. Rev. Lett. 108, 253005 (2012)] proposed a scheme that may be called HOMO depopulation. In this study, we tested this scheme on an extensive dataset of valence and Rydberg excitation energies of various atoms, ions, and molecules. It is also tested on a charge-transfer excitation of NH{sub 3}-F{sub 2} and on the potentialmore »« less
https://doi.org/10.1063/1.4894522
A New, Self-Contained Asymptotic Correction Scheme To Exchange-Correlation Potentials For Time-Dependent Density Functional Theory

Journal Article Hirata, So ; Zhan, Chang-Guo ; Apra, Edoardo ; ... - Journal of Physical Chemistry A, 107(10154-10158

By combining the asymptotic correction scheme of Casida and Salahub to exchange cor-relation potentials and the phenomenological linear correlation between experimental ionization potentials and highest occupied Kohn–Sham (KS) orbital energies found by Zhan, Nichols, and Dixon, we propose a new, expedient, and self-contained asymptotic correction to exchange-correlation potentials in KS density functional theory (DFT) for use in time-dependent density functional theory (TDDFT) that does not require an ionization potential as an external parameter from a separate calculation. The asymptotically-corrected (TD)DFT is implemented in the quan-tum chemistry program suite NWChem for both sequential and massively parallel execution. The method is shownmore »« less
https://doi.org/10.1021/jp035667x
Density Functionals with Broad Applicability in Chemistry

Journal Article Zhao, Yan ; Truhlar, Donald G - Accounts of Chemical Research, 41(2):157-167

The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Although density functional theory is widely used in the computational chemistry community, the most popular density functional, B3LYP, has some serious shortcomings: (i) it is better for main-group chemistry than for transition metals; (ii) it systematically underestimates reaction barrier heights; (iii) it is inaccurate for interactions dominated by mediumrange correlation energy, such as van der Waals attraction, aromatic-aromatic stacking, andmore »« less
https://doi.org/10.1021/ar700111a
Importance of imposing gauge invariance in time-dependent density functional theory calculations with meta-generalized gradient approximations

Journal Article Grotjahn, Robin ; Furche, Filipp ; Kaupp, Martin - Journal of Chemical Physics

It has been known for more than a decade that the gauge variance of the kinetic energy density τ leads to additional terms in the magnetic orbital rotation Hessian used in linear-response time-dependent density functional theory (TDDFT), affecting excitation energies obtained with τ-dependent exchange–correlation functionals. While previous investigations found that a correction scheme based on the paramagnetic current density has a small effect on benchmark results, we report more pronounced effects here, in particular, for the popular M06-2X functional and for some other meta-generalized gradient approximations (mGGAs). In the first part of this communication, this is shown by a reassessmentmore »« less
https://doi.org/10.1063/5.0113083

Full Text Available
Analytic energy gradient of excited electronic state within TDDFT/MMpol framework: Benchmark tests and parallel implementation

Journal Article Zeng, Qiao ; Liang, WanZhen - Journal of Chemical Physics

The time-dependent density functional theory (TDDFT) has become the most popular method to calculate the electronic excitation energies, describe the excited-state properties, and perform the excited-state geometric optimization of medium and large-size molecules due to the implementation of analytic excited-state energy gradient and Hessian in many electronic structure software packages. To describe the molecules in condensed phase, one usually adopts the computationally efficient hybrid Quantum Mechanics/Molecular Mechanics (QM/MM) models. Here, we extend our previous work on the energy gradient of TDDFT/MM excited state to account for the mutual polarization effects between QM and MM regions, which is believed to holdmore »« less
https://doi.org/10.1063/1.4931734

Similar Records

Title: Improving Rydberg Excitations within Time-Dependent Density Functional Theory with Generalized Gradient Approximations: The Exchange-Enhancement-for-Large-Gradient Scheme

Abstract

Citation Formats

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

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

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

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