Time-Dependent Second-Order Green's Function Theory for Neutral Excitations

Wenjie Dou; Joonho Lee; Jian Zhu; Leopoldo Mejía; David R. Reichman; Roi Baer; Eran Rabani

doi:10.1021/acs.jctc.2c00057

Time-Dependent Second-Order Green's Function Theory for Neutral Excitations

Wenjie Dou^*, Joonho Lee^*, Jian Zhu^*, Leopoldo Mejía^*, David R. Reichman^*, Roi Baer^*, Eran Rabani^*

^*Corresponding author for this work

Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

We develop a time-dependent second-order Green's function theory (GF2) for calculating neutral excited states in molecules. The equation of motion for the lesser Green's function (GF) is derived within the adiabatic approximation to the Kadanoff-Baym (KB) equation, using the second-order Born approximation for the self-energy. In the linear response regime, we recast the time-dependent KB equation into a Bethe-Salpeter-like equation (GF2-BSE), with a kernel approximated by the second-order Coulomb self-energy. We then apply our GF2-BSE to a set of molecules and atoms and find that GF2-BSE is superior to configuration interaction with singles (CIS) and/or time-dependent Hartree-Fock (TDHF), particularly for charge-transfer excitations, and is comparable to CIS with perturbative doubles (CIS(D)) in most cases.

Original language	English
Pages (from-to)	5221-5232
Number of pages	12
Journal	Journal of Chemical Theory and Computation
Volume	18
Issue number	9
DOIs	https://doi.org/10.1021/acs.jctc.2c00057
State	Published - 13 Sep 2022

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title = "Time-Dependent Second-Order Green's Function Theory for Neutral Excitations",

abstract = "We develop a time-dependent second-order Green's function theory (GF2) for calculating neutral excited states in molecules. The equation of motion for the lesser Green's function (GF) is derived within the adiabatic approximation to the Kadanoff-Baym (KB) equation, using the second-order Born approximation for the self-energy. In the linear response regime, we recast the time-dependent KB equation into a Bethe-Salpeter-like equation (GF2-BSE), with a kernel approximated by the second-order Coulomb self-energy. We then apply our GF2-BSE to a set of molecules and atoms and find that GF2-BSE is superior to configuration interaction with singles (CIS) and/or time-dependent Hartree-Fock (TDHF), particularly for charge-transfer excitations, and is comparable to CIS with perturbative doubles (CIS(D)) in most cases.",

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AU - Dou, Wenjie

AU - Lee, Joonho

AU - Zhu, Jian

AU - Mejía, Leopoldo

AU - Reichman, David R.

AU - Baer, Roi

AU - Rabani, Eran

PY - 2022/9/13

Y1 - 2022/9/13

N2 - We develop a time-dependent second-order Green's function theory (GF2) for calculating neutral excited states in molecules. The equation of motion for the lesser Green's function (GF) is derived within the adiabatic approximation to the Kadanoff-Baym (KB) equation, using the second-order Born approximation for the self-energy. In the linear response regime, we recast the time-dependent KB equation into a Bethe-Salpeter-like equation (GF2-BSE), with a kernel approximated by the second-order Coulomb self-energy. We then apply our GF2-BSE to a set of molecules and atoms and find that GF2-BSE is superior to configuration interaction with singles (CIS) and/or time-dependent Hartree-Fock (TDHF), particularly for charge-transfer excitations, and is comparable to CIS with perturbative doubles (CIS(D)) in most cases.

AB - We develop a time-dependent second-order Green's function theory (GF2) for calculating neutral excited states in molecules. The equation of motion for the lesser Green's function (GF) is derived within the adiabatic approximation to the Kadanoff-Baym (KB) equation, using the second-order Born approximation for the self-energy. In the linear response regime, we recast the time-dependent KB equation into a Bethe-Salpeter-like equation (GF2-BSE), with a kernel approximated by the second-order Coulomb self-energy. We then apply our GF2-BSE to a set of molecules and atoms and find that GF2-BSE is superior to configuration interaction with singles (CIS) and/or time-dependent Hartree-Fock (TDHF), particularly for charge-transfer excitations, and is comparable to CIS with perturbative doubles (CIS(D)) in most cases.

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ER -

Time-Dependent Second-Order Green's Function Theory for Neutral Excitations

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