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Title: Approximate singly excited states from a two-component Hartree-Fock reference

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4932540· OSTI ID:22489693
; ; ;  [1]
  1. Department of Chemistry, University of Washington, Seattle, Washington 98195 (United States)
+ Show Author Affiliations

For many molecules, relaxing the spin symmetry constraint on the wave function results in the lowest energy mean-field solution. The two-component Hartree-Fock (2cHF) method relaxes all spin symmetry constraints, and the wave function is no longer an eigenfunction of the total spin, spin projection, or time-reversal symmetry operators. For ground state energies, 2cHF is a superior mean-field method for describing spin-frustrated molecules. For excited states, the utility of 2cHF is uncertain. Here, we implement the 2cHF extensions of two single-reference excited state methods, the two-component configuration interaction singles and time-dependent Hartree-Fock. We compare the results to the analogous methods based off of the unrestricted Hartree-Fock approximation, as well as the full configuration interaction for three small molecules with distinct 2cHF solutions, and discuss the nature of the 2cHF excited state solutions.

OSTI ID:
22489693
Journal Information:
Journal of Chemical Physics, Vol. 143, Issue 14; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
Country of Publication:
United States
Language:
English

References (37)

Noncollinear spin density functional theory for spin-frustrated and spin-degenerate systems journal January 2001
Unrestricted Hartree-Fock theory and its applications to molecules and chemical reactions journal November 1981
Psi4: an open-source ab initio electronic structure program : Psi4: an electronic structure program
  • Turney, Justin M.; Simmonett, Andrew C.; Parrish, Robert M.
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 4 https://doi.org/10.1002/wcms.93
journal October 2011
Quantum electrodynamical corrections to the fine structure of helium journal January 1974
Some Studies of the General Hartree-Fock Method book January 1992
Single-Reference ab Initio Methods for the Calculation of Excited States of Large Molecules journal November 2005
A New Approach to Noncollinear Spin Density Functional Theory beyond the Local Density Approximation journal June 2012
Implementation of Two-Component Time-Dependent Density Functional Theory in TURBOMOLE journal November 2013
Noncollinear Spin States for Density Functional Calculations of Open-Shell and Multi-Configurational Systems: Dissociation of MnO and NiO and Barrier Heights of O 3 , BeH 2 , and H 4 journal November 2013
Testing Noncollinear Spin-Flip, Collinear Spin-Flip, and Conventional Time-Dependent Density Functional Theory for Predicting Electronic Excitation Energies of Closed-Shell Atoms journal April 2014
Polyradical Character and Spin Frustration in Fullerene Molecules: An Ab Initio Non-Collinear Hartree–Fock Study journal October 2014
Noncollinear Spins Provide a Self-Consistent Treatment of the Low-Spin State of a Biomimetic Oxomanganese Synthetic Trimer Inspired by the Oxygen Evolving Complex of Photosystem II journal October 2011
Interfacing relativistic and nonrelativistic methods. IV. One- and two-electron scalar approximations journal November 2001
Oscillator Strengths and Rotational Strengths in Hartree–Fock Theory journal May 1969
Self‐consistent molecular orbital methods. XVIII. Constraints and stability in Hartree–Fock theory journal April 1977
The two‐electron terms of the no‐pair Hamiltonian journal January 1992
Projected Hartree–Fock theory journal April 2012
Interfacing relativistic and nonrelativistic methods. I. Normalized elimination of the small component in the modified Dirac equation journal June 1997
Interfacing relativistic and nonrelativistic methods. II. Investigation of a low-order approximation journal September 1998
Interfacing relativistic and nonrelativistic methods. III. Atomic 4-spinor expansions and integral approximations journal December 1999
Proper and improper zero energy modes in Hartree-Fock theory and their relevance for symmetry breaking and restoration journal October 2013
Multi-component symmetry-projected approach for molecular ground state correlations journal November 2013
Excited electronic states from a variational approach based on symmetry-projected Hartree–Fock configurations journal December 2013
Time-dependent projected Hartree-Fock journal March 2015
Stability of the complex generalized Hartree-Fock equations journal April 2015
Non-collinear magnetism induced by frustration in transition-metal nanostructures deposited on surfaces journal June 2014
Applicability of the no-pair equation with free-particle projection operators to atomic and molecular structure calculations journal August 1985
Multireference symmetry-projected variational approaches for ground and excited states of the one-dimensional Hubbard model journal June 2013
Symmetry-projected wave functions in quantum Monte Carlo calculations journal March 2014
Multireference symmetry-projected variational approximation for the ground state of the doped one-dimensional Hubbard model journal May 2014
Time-Dependent Hartree—Fock Theory for Molecules journal July 1964
Single-Reference ab initio Methods for the Calculation of Excited States of Large Molecules journal January 2006
Multi-reference symmetry-projected variational approaches for ground and excited states of the one-dimensional Hubbard model text January 2013
Multi-component symmetry-projected approach for molecular ground state correlations text January 2013
Excited electronic states from a variational approach based on symmetry-projected Hartree--Fock configurations text January 2013
Symmetry-projected Wave Functions in Quantum Monte Carlo Calculations text January 2014
Non-collinear magnetism induced by frustration in transition-metal nanostructures deposited on surfaces text January 2014

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37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
97 MATHEMATICAL METHODS AND COMPUTING
COMPARATIVE EVALUATIONS
EIGENFUNCTIONS
EXCITED STATES
GROUND STATES
HARTREE-FOCK METHOD
MATHEMATICAL SOLUTIONS
MEAN-FIELD THEORY
MOLECULES
SPIN
TIME DEPENDENCE
WAVE FUNCTIONS