论文标题
受时间依赖电场的溶质分子实时电子动力学中的非平衡溶剂极化效应：可极化连续模型的新特征
Nonequilibrium Solvent Polarization Effects in Real-Time Electronic Dynamics of Solute Molecules Subject to Time-Dependent Electric Fields: A New Feature of the Polarizable Continuum Model
论文作者
论文摘要
我们开发了时间依赖性方程式公式的扩展，可极化连续元模型（EOM-TDPCM）在溶剂化分子的量子机械计算中引入非平衡腔场效应，但受时间依赖电场的溶剂分子。该方法已在章鱼中实现，章鱼是一种实时空间，实时时间相关密度功能理论（RT-TDDFT）计算的最新代码。为了显示我们的方法的潜力，我们对水中的反偶亚苯和其他模型溶剂进行了EOM-TDPCM/RT-TDDFT计算，其松弛时间较短。我们对反偶亚苯的光吸收光谱的结果表明（i）表明，空腔场效应在整体光谱形状上具有明显的影响，并且（ii）（ii）对溶质形状的准确描述（如PCM中提供的溶质形状）是正确说明空腔场效应的关键。
We develop an extension of the time-dependent equation-of-motion formulation of the polarizable continuum model (EOM-TDPCM) to introduce nonequilibrium cavity field effects in quantum mechanical calculations of solvated molecules subject to time-dependent electric fields. This method has been implemented in Octopus, a state-of-the-art code for real-space, real-time time-dependent density functional theory (RT-TDDFT) calculations. To show the potential of our methodology, we perform EOM-TDPCM/RT-TDDFT calculations of trans-azobenzene in water and in other model solvents with shorter relaxation times. Our results for the optical absorption spectrum of trans-azobenzene show (i) that cavity field effects have a clear impact in the overall spectral shape and (ii) that an accurate description of the solute shape (as the one provided within PCM) is key to correctly account for cavity field effects.
