{"title":"来自 GW 和 Hartree-Fock 理论的分子电离能:极化性、筛选和自能顶点校正。","authors":"Charles H Patterson","doi":"10.1021/acs.jctc.4c00795","DOIUrl":null,"url":null,"abstract":"<p><p>Accurate prediction of electron removal and addition energies is essential for reproducing neutral excitation spectra in molecules using Bethe-Salpeter equation methods. A Hartree-Fock starting point for <i>GW</i>/BSE calculations, combined with a random phase approximation (RPA) polarizability in the screened interaction, <i>W</i>, is well-known to overestimate neutral excitation energies. Using a Hartree-Fock starting point, we apply several different approximations for <i>W</i> to molecules in the Quest-3 database [Loos et al. <i>J. Chem. Theory Comput.</i> <b>2020</b>, <i>16</i>, 1711]. <i>W</i> is calculated using polarizabilities in RPA and time-dependent HF approximations. Inclusion of screened electron-hole attraction in the polarizability yields valence ionization energies in better agreement with experimental values and ADC(3) calculations than the more commonly applied RPA polarizability. Quasiparticle weights are also in better agreement with ADC(3) values when electron-hole attraction is included in <i>W</i>. Shake-up excitations for the 1π levels in benzene and azines are indicated only when electron-hole attraction is included. Ionization energies derived from HF eigenvalues via Koopmans theorem for molecules with nitrogen or oxygen lone pairs have the largest differences from experimental values in the molecules considered, leading to incorrect ordering of nonbonding and π bonding levels. Inclusion of electron-hole attraction in the polarizability results in correct ordering of ionization energies and marked improvement in agreement with experimental data. Vertex corrections to the self-energy further improve agreement with experimental ionization energies for these localized states.</p>","PeriodicalId":45,"journal":{"name":"Journal of Chemical Theory and Computation","volume":null,"pages":null},"PeriodicalIF":5.7000,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11391582/pdf/","citationCount":"0","resultStr":"{\"title\":\"Molecular Ionization Energies from GW and Hartree-Fock Theory: Polarizability, Screening, and Self-Energy Vertex Corrections.\",\"authors\":\"Charles H Patterson\",\"doi\":\"10.1021/acs.jctc.4c00795\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Accurate prediction of electron removal and addition energies is essential for reproducing neutral excitation spectra in molecules using Bethe-Salpeter equation methods. A Hartree-Fock starting point for <i>GW</i>/BSE calculations, combined with a random phase approximation (RPA) polarizability in the screened interaction, <i>W</i>, is well-known to overestimate neutral excitation energies. Using a Hartree-Fock starting point, we apply several different approximations for <i>W</i> to molecules in the Quest-3 database [Loos et al. <i>J. Chem. Theory Comput.</i> <b>2020</b>, <i>16</i>, 1711]. <i>W</i> is calculated using polarizabilities in RPA and time-dependent HF approximations. Inclusion of screened electron-hole attraction in the polarizability yields valence ionization energies in better agreement with experimental values and ADC(3) calculations than the more commonly applied RPA polarizability. Quasiparticle weights are also in better agreement with ADC(3) values when electron-hole attraction is included in <i>W</i>. Shake-up excitations for the 1π levels in benzene and azines are indicated only when electron-hole attraction is included. Ionization energies derived from HF eigenvalues via Koopmans theorem for molecules with nitrogen or oxygen lone pairs have the largest differences from experimental values in the molecules considered, leading to incorrect ordering of nonbonding and π bonding levels. Inclusion of electron-hole attraction in the polarizability results in correct ordering of ionization energies and marked improvement in agreement with experimental data. 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引用次数: 0
摘要
要利用贝特-萨尔佩特方程方法再现分子中的中性激发光谱,就必须准确预测电子移除和添加能量。众所周知,GW/BSE 计算的哈特里-福克起点结合屏蔽相互作用中的随机相近似(RPA)极化率 W 会高估中性激发能量。利用哈特里-福克起点,我们对 Quest-3 数据库 [Loos 等人,J. Chem. Theory Comput.]我们使用 RPA 和随时间变化的高频近似中的极化率计算 W。与更常用的 RPA 极化率相比,在极化率中加入屏蔽电子-空穴吸引力可得到与实验值和 ADC(3) 计算更一致的价电离能。当 W 中包含电子-空穴吸引力时,准粒子权重与 ADC(3) 值的一致性也更好。对于具有氮或氧孤对子的分子,通过库普曼(Koopmans)定理从高频特征值推导出的电离能与实验值的差异最大,导致非键级和π键级的排序不正确。在极化率中加入电子-空穴吸引力会导致电离能的正确排序,并明显改善与实验数据的一致性。对自能的顶点修正进一步提高了这些局域态与实验电离能的一致性。
Molecular Ionization Energies from GW and Hartree-Fock Theory: Polarizability, Screening, and Self-Energy Vertex Corrections.
Accurate prediction of electron removal and addition energies is essential for reproducing neutral excitation spectra in molecules using Bethe-Salpeter equation methods. A Hartree-Fock starting point for GW/BSE calculations, combined with a random phase approximation (RPA) polarizability in the screened interaction, W, is well-known to overestimate neutral excitation energies. Using a Hartree-Fock starting point, we apply several different approximations for W to molecules in the Quest-3 database [Loos et al. J. Chem. Theory Comput.2020, 16, 1711]. W is calculated using polarizabilities in RPA and time-dependent HF approximations. Inclusion of screened electron-hole attraction in the polarizability yields valence ionization energies in better agreement with experimental values and ADC(3) calculations than the more commonly applied RPA polarizability. Quasiparticle weights are also in better agreement with ADC(3) values when electron-hole attraction is included in W. Shake-up excitations for the 1π levels in benzene and azines are indicated only when electron-hole attraction is included. Ionization energies derived from HF eigenvalues via Koopmans theorem for molecules with nitrogen or oxygen lone pairs have the largest differences from experimental values in the molecules considered, leading to incorrect ordering of nonbonding and π bonding levels. Inclusion of electron-hole attraction in the polarizability results in correct ordering of ionization energies and marked improvement in agreement with experimental data. Vertex corrections to the self-energy further improve agreement with experimental ionization energies for these localized states.
期刊介绍:
The Journal of Chemical Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere. Papers reporting new theories, methodology, and/or important applications in quantum electronic structure, molecular dynamics, and statistical mechanics are appropriate for submission to this Journal. Specific topics include advances in or applications of ab initio quantum mechanics, density functional theory, design and properties of new materials, surface science, Monte Carlo simulations, solvation models, QM/MM calculations, biomolecular structure prediction, and molecular dynamics in the broadest sense including gas-phase dynamics, ab initio dynamics, biomolecular dynamics, and protein folding. The Journal does not consider papers that are straightforward applications of known methods including DFT and molecular dynamics. The Journal favors submissions that include advances in theory or methodology with applications to compelling problems.