Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, USA.
Department of Chemistry and Chemical Biology, University of California, Merced, California 95343, USA; email:
Annu Rev Phys Chem. 2021 Apr 20;72:165-188. doi: 10.1146/annurev-physchem-090419-051350. Epub 2021 Jan 4.
Including both environmental and vibronic effects is important for accurate simulation of optical spectra, but combining these effects remains computationally challenging. We outline two approaches that consider both the explicit atomistic environment and the vibronic transitions. Both phenomena are responsible for spectral shapes in linear spectroscopy and the electronic evolution measured in nonlinear spectroscopy. The first approach utilizes snapshots of chromophore-environment configurations for which chromophore normal modes are determined. We outline various approximations for this static approach that assumes harmonic potentials and ignores dynamic system-environment coupling. The second approach obtains excitation energies for a series of time-correlated snapshots. This dynamic approach relies on the accurate truncation of the cumulant expansion but treats the dynamics of the chromophore and the environment on equal footing. Both approaches show significant potential for making strides toward more accurate optical spectroscopy simulations of complex condensed phase systems.
包括环境和振子相互作用对于准确模拟光学光谱非常重要，但结合这些效应在计算上仍然具有挑战性。我们概述了两种方法，这两种方法都考虑了明确的原子环境和振子跃迁。这两种现象都对线性光谱中的光谱形状以及非线性光谱中测量的电子演化负责。第一种方法利用发色团环境构象的快照，其中确定发色团的正则模态。我们概述了这种静态方法的各种近似方法，该方法假设了谐波势并且忽略了动态系统环境耦合。第二种方法为一系列时相关快照获得激发能量。这种动态方法依赖于对累积展开的精确截断，但平等对待发色团和环境的动力学。这两种方法都为更准确地模拟复杂凝聚相系统的光学光谱迈出了重要的一步。
