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:https://doi.org/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

Tel Aviv University, The Hebrew University of Jerusalem

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

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

All Science Journal Classification (ASJC) codes

Computer Science Applications
Physical and Theoretical Chemistry

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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.",

author = "Wenjie Dou and Joonho Lee and Jian Zhu and Leopoldo Mej{\'i}a and Reichman, {David R.} and Roi Baer and Eran Rabani",

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TY - JOUR

T1 - Time-Dependent Second-Order Green's Function Theory for Neutral Excitations

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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U2 - https://doi.org/10.1021/acs.jctc.2c00057

DO - https://doi.org/10.1021/acs.jctc.2c00057

M3 - مقالة

C2 - 36040050

SN - 1549-9618

VL - 18

SP - 5221

EP - 5232

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

IS - 9

ER -

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

Abstract

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