Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, Tokyo 169-8555, Japan.
J Chem Phys. 2010 Feb 7;132(5):054104. doi: 10.1063/1.3300127.
We propose a novel analysis of real-time (RT) time-dependent Hartree-Fock and time-dependent density functional theory (TDHF/TDDFT) calculations using a short-time Fourier transform (STFT) technique. RT-TDHF/TDDFT calculations of model dimers were carried out and analyzed using the STFT technique, in addition to the usual Fourier transform (FT). STFT analysis revealed that the induced polarization propagated between the molecules through the intermolecular interaction; that is, it directly showed the electron dynamics of the excited system. The dependence of the propagation period on the intermolecular distance of the dimer was investigated. We also proved the possibility of describing, not just the valence, but also the core excitations by FT analysis of the RT-TDHF/TDDFT calculations of a formaldehyde monomer with Gaussian basis functions compared with conventional TDHF/TDDFT results.
我们提出了一种使用短时傅里叶变换（STFT）技术对实时（RT）时变Hartree-Fock 和时变密度泛函理论（TDHF/TDDFT）计算进行新分析的方法。除了通常的傅里叶变换（FT）之外，我们还使用 STFT 技术对模型二聚体的 RT-TDHF/TDDFT 计算进行了分析。STFT 分析表明，诱导极化通过分子间相互作用在分子之间传播；也就是说，它直接显示了激发系统的电子动力学。我们还研究了传播周期对二聚体分子间距离的依赖性。与传统的 TDHF/TDDFT 结果相比，我们还通过比较使用高斯基函数的甲醛单体的 RT-TDHF/TDDFT 计算的 FT 分析证明了不仅可以描述价态，还可以描述核心激发的可能性。
