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Title: Gentlest ascent dynamics for calculating first excited state and exploring energy landscape of Kohn-Sham density functionals

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4936411· OSTI ID:1371102
ORCiD logo [1];  [1];  [2]
  1. Duke Univ., Durham, NC (United States)
  2. Duke Univ., Durham, NC (United States); South China Normal Univ., Guangzhou (China)
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Here, we develop the gentlest ascent dynamics for Kohn-Sham density functional theory to search for the index-1 saddle points on the energy landscape of the Kohn-Sham density functionals. These stationary solutions correspond to excited states in the ground state functionals. As shown by various examples, the first excited states of many chemical systems are given by these index-1 saddle points. Our novel approach provides an alternative, more robust way to obtain these excited states, compared with the widely used ΔSCF approach. The method can be easily generalized to target higher index saddle points. Our results also reveal the physical interest and relevance of studying the Kohn-Sham energy landscape.

Research Organization:
Energy Frontier Research Centers (EFRC), Washington, D.C. (United States). Center for the Computational Design of Functional Layered Materials (CCDM)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012575
OSTI ID:
1371102
Alternate ID(s):
OSTI ID: 1228787
Journal Information:
Journal of Chemical Physics, Vol. 143, Issue 22; Related Information: CCDM partners with Temple University (lead); Brookhaven National Laboratory; Drexel University; Duke University; North Carolina State University; Northeastern University; Princeton University; Rice University; University of Pennsylvania; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

References (55)

Dynamical dimer method for the determination of transition states with ab initio molecular dynamics journal January 2008
A linear response, coupled-cluster theory for excitation energy journal March 1984
Event-Based Relaxation of Continuous Disordered Systems journal November 1996
The implementation of a self-consistent constricted variational density functional theory for the description of excited states journal March 2012
Efficient Sampling of Saddle Points with the Minimum-Mode Following Method journal January 2011
Local density-functional theory of frequency-dependent linear response journal December 1985
Density-functional exchange-energy approximation with correct asymptotic behavior journal September 1988
On some approximations in applications of X α theory journal October 1979
An extension of the coupled cluster formalism to excited states (I) journal January 1981
Extrema of the density functional for the energy: Excited states from the ground-state theory journal May 1985
A multireference perturbation method using non-orthogonal Hartree-Fock determinants for ground and excited states journal November 2013
On finding transition states journal September 1981
Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis journal August 1980
The energy density functional formalism for excited states journal December 1979
The formulation of a self-consistent constricted variational density functional theory for the description of excited states journal November 2011
Self-consistent-field calculations of core excited states journal March 2009
Rayleigh-Ritz variational principle for ensembles of fractionally occupied states journal April 1988
Applications of Time-Dependent and Time-Independent Density Functional Theory to Rydberg Transitions journal October 2014
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives journal October 1999
Self‐consistent molecular orbital methods. XVIII. Constraints and stability in Hartree–Fock theory journal April 1977
Unified Approach for Molecular Dynamics and Density-Functional Theory journal November 1985
Defect migration in crystalline silicon journal February 1999
The Application of Constricted Variational Density Functional Theory to Excitations Involving Electron Transitions from Occupied Lone-Pair Orbitals to Virtual π* Orbitals journal June 2011
Self-Consistent Equations Including Exchange and Correlation Effects journal November 1965
Minimization of polypeptide energy journal June 1971
Orthogonality Constrained Density Functional Theory for Electronic Excited States journal May 2013
Time-independent (static) density-functional theories for pure excited states: Extensions and unification journal July 2009
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Single-Reference ab Initio Methods for the Calculation of Excited States of Large Molecules journal November 2005
Core-ionized and core-excited states of macromolecules journal January 2007
Variational Density-Functional Theory for an Individual Excited State journal November 1999
Application of the local self-consistent-field method to core-ionized and core-excited molecules, polymers, and proteins: True orthogonality between ground and excited states journal September 2002
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
Ab initio Hartree-Fock instabilities in closed-shell molecular systems journal May 1978
On the calculation of multiplet energies by the hartree-fock-slater method journal January 1977
Generalized Kohn-Sham theory for electronic excitations in realistic systems journal March 1986
Comparison of methods for finding saddle points without knowledge of the final states journal November 2004
Perspective: Fifty years of density-functional theory in chemical physics journal May 2014
Assessment of the ΔSCF density functional theory approach for electronic excitations in organic dyes journal February 2011
Rydberg energies using excited state density functional theory journal September 2008
Density-Functional Theory for Time-Dependent Systems journal March 1984
Stability Conditions for the Solutions of the Hartree—Fock Equations for Atomic and Molecular Systems. Application to the Pi‐Electron Model of Cyclic Polyenes journal November 1967
The equation-of-motion coupled-cluster method: Excitation energies of Be and CO journal December 1989
Assessment of Gaussian-2 and density functional theories for the computation of enthalpies of formation journal January 1997
Molecular Dynamics and ab initio Total Energy Calculations journal June 1986
On the relation between time-dependent and variational density functional theory approaches for the determination of excitation energies and transition moments. journal April 2009
Stability analysis for solutions of the closed shell Kohn–Sham equation journal June 1996
Communication: Hartree-Fock description of excited states of H 2 journal September 2014
Atomistic simulations of rare events using gentlest ascent dynamics journal March 2012
The gentlest ascent dynamics journal May 2011
Present and future trends in quantum chemical calculations journal December 1988
Time-independent density-functional theory for excited states of Coulomb systems journal April 2012
Locating Multiple Self-Consistent Field Solutions: An Approach Inspired by Metadynamics journal November 2008
Integral approximations for LCAO-SCF calculations journal October 1993
Applicability of the multi-reference double-excitation CI (MRD-CI) method to the calculation of electronic wavefunctions and comparison with related techniques journal March 1978

Figures / Tables (5)

FIG. 1(p. 6)figure FIG. 1
TABLE I(p. 6)table TABLE I
TABLE II(p. 7)table TABLE II
TABLE III(p. 8)table TABLE III
TABLE IV(p. 8)table TABLE IV

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