Donati Greta, Wildman Andrew, Caprasecca Stefano, Lingerfelt David B, Lipparini Filippo, Mennucci Benedetta, Li Xiaosong
Department of Chemistry, University of Washington , Seattle, Washington 98195, United States.
Dipartimento di Chimica e Chimica Industriale, Università di Pisa , Via G. Moruzzi 13, 56124 Pisa, Italy.
J Phys Chem Lett. 2017 Nov 2;8(21):5283-5289. doi: 10.1021/acs.jpclett.7b02320. Epub 2017 Oct 13.
Real-time time-dependent density functional theory (RT-TDDFT) is a powerful tool for obtaining spectroscopic observables and understanding complex, time-dependent properties. Currently, performing RT-TDDFT calculations on large, fully quantum mechanical systems is not computationally feasible. Previously, polarizable mixed quantum mechanical and molecular mechanical (QM/MMPol) models have been successful in providing accurate, yet efficient, approximations to a fully quantum mechanical system. Here we develop a coupling scheme between induced dipole based QM/MMPol and RT-TDDFT. Our approach is validated by comparing calculated spectra with both real-time and linear-response TDDFT calculations. The model developed within provides an accurate method for performing RT-TDDFT calculations on extended systems while accounting for mutual polarization between the quantum mechanical and molecular mechanical regions.
实时含时密度泛函理论（RT-TDDFT）是获取光谱可观测量以及理解复杂含时性质的有力工具。目前，对大型全量子力学系统进行RT-TDDFT计算在计算上是不可行的。此前，可极化混合量子力学与分子力学（QM/MMPol）模型已成功地为全量子力学系统提供了准确而高效的近似。在此，我们开发了一种基于诱导偶极子的QM/MMPol与RT-TDDFT之间的耦合方案。我们通过将计算光谱与实时和线性响应TDDFT计算结果进行比较来验证我们的方法。在此开发的模型提供了一种在考虑量子力学区域和分子力学区域之间的相互极化的同时，对扩展系统进行RT-TDDFT计算的准确方法。
