Pedersen Jacob, Sannes Bendik Støa, Paul Née Matveeva Regina, Coriani Sonia, Høyvik Ida-Marie
Department of Chemistry, Technical University of Denmark, DK-2800 Kongens Lyngby, Denmark.
Department of Chemistry, Norwegian University of Science and Technology, N-7491 Trondheim, Norway.
J Phys Chem A. 2025 May 15;129(19):4288-4300. doi: 10.1021/acs.jpca.5c00810. Epub 2025 May 1.
We develop the time-dependent particle-breaking Hartree-Fock (TDPBHF) model to describe excited states and linear response properties of electronically open molecules. This work represents the first step toward building a wave function-based response theory framework for electronically open quantum systems equivalent to that of closed quantum systems. In the limit of particle conservation, TDPBHF reduces to standard time-dependent Hartree-Fock theory. We illustrate the TDPBHF model by computing valence absorption spectra and frequency-dependent electric dipole polarizabilities for a set of small- to medium-sized organic molecules. The particle-breaking interactions are observed to nonuniformly redshift the excitation energies and induce qualitative changes in the absorption profile. In addition, the mixing of multiple excitations in the TDPBHF wave function is observed to dampen the divergence of the response function in the vicinity of resonance energies.
我们开发了含时粒子破裂哈特里-福克（TDPBHF）模型来描述电子开放分子的激发态和线性响应特性。这项工作是朝着构建一个基于波函数的响应理论框架迈出的第一步，该框架适用于与封闭量子系统等效的电子开放量子系统。在粒子守恒的极限情况下，TDPBHF简化为标准的含时哈特里-福克理论。我们通过计算一组中小尺寸有机分子的价吸收光谱和频率相关的电偶极极化率来说明TDPBHF模型。观察到粒子破裂相互作用会使激发能非均匀地红移，并在吸收谱中引起定性变化。此外，观察到TDPBHF波函数中多个激发的混合会抑制响应函数在共振能量附近的发散。
