Curing the Divergence in Time-Dependent Density Functional Quadratic Response Theory

被引：0

作者：

Dar, Davood ^{[1
]}

Roy, Saswata ^{[1
]}

Maitra, Neepa T. ^{[1
]}

机构：

[1] Rutgers State Univ, Dept Phys, Newark, NJ 07102 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2023年 / 14卷 / 13期

基金：

美国国家科学基金会;

关键词：

EXCITED-STATES; DERIVATIVE COUPLINGS; EXCITATION-ENERGIES; NONLINEAR-RESPONSE;

D O I：

10.1021/acs.jpclett.3c001223186J

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The adiabatic approximation in time-dependent density functional theory is known to give an incorrect pole structure in the quadratic response function, leading to unphysical divergences in excited state-to-state transition probabilities and hyperpolarizabilties. We find the form of the exact quadratic response kernel and derive a practical and accurate approximation that cures the divergence. We demonstrate our results on excited state-to-state transition probabilities of a model system and of the LiH molecule.

引用

页码：3186 / 3192

页数：7

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