Peng Daoling, Li Shaopeng, Peng Liang, Gu Feng Long, Yang Weitao
Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education; School of Chemistry and Environment, South China Normal University , Guangzhou 510006, China.
Department of Chemistry, Duke University , Box 90346, Durham, North Carolina 27708-0346, United States.
J Chem Theory Comput. 2017 Sep 12;13(9):4101-4112. doi: 10.1021/acs.jctc.7b00321. Epub 2017 Aug 25.
The time-dependent coupled perturbed Hartree-Fock/density-functional-theory (TDHF/TDDFT) approach has been reformulated based on nonorthogonal localized molecular orbitals (NOLMOs). Based on the NOLMO Fock equation, we have derived the corresponding NOLMO-TDHF/TDDFT equations up to the third order, and the formula for the frequency-dependent (hyper)polarizabilities has been given. Our approach has been applied to calculate both static and dynamic (hyper)polarizabilities of molecules varying from small molecules to large molecules. The NOLMO-TDHF/TDDFT approach can reproduce the reference canonical molecular orbital (CMO) results for all of our testing calculations. With the help of ongoing development of optimized local virtual molecular orbitals, the NOLMO-TDHF/TDDFT approach would be a very efficient method for large system calculations and tp achieve linear scaling.
基于非正交定域分子轨道（NOLMOs），对含时耦合微扰Hartree-Fock/密度泛函理论（TDHF/TDDFT）方法进行了重新表述。基于NOLMO福克方程，我们推导了直至三阶的相应NOLMO-TDHF/TDDFT方程，并给出了频率相关（超）极化率的公式。我们的方法已应用于计算从小分子到大分子等不同分子的静态和动态（超）极化率。对于我们所有的测试计算，NOLMO-TDHF/TDDFT方法都能重现参考正则分子轨道（CMO）的结果。借助不断发展的优化局域虚拟分子轨道，NOLMO-TDHF/TDDFT方法将成为一种用于大体系计算并实现线性标度的非常有效的方法。
