论文标题
耦合电子和分子量子化学的振动
Coupling electrons and vibrations in molecular quantum chemistry
论文作者
论文摘要
我们在量子化学框架中得出了一种电子振动模型，并探索这种哈密顿量可以捕获非绝热动力学的关键影响的程度。 Hamiltonian模型是一个简单的两体操作员，我们在应用标准量子化学方法评估其性质的初步步骤中，包括平均场理论，线性响应和原始相关模型。可以将哈密顿量与标准振动性哈密顿量进行比较，但通过在单个参考几何形状上直接分化一单元和两电子积分，而无需参考势能表面。吡嗪在谐波和线性耦合方面进行了模型hamiltonian的性质，其中证明了一个简单的时间依赖时间计算，包括电子振动相关性，以表现出S $ _2 $和S $ _1 $ _1 $兴奋的状态之间良好的种群转移。
We derive an electron-vibration model Hamiltonian in a quantum chemical framework, and explore the extent to which such a Hamiltonian can capture key effects of nonadiabatic dynamics. The model Hamiltonian is a simple two-body operator, and we make preliminary steps at applying standard quantum chemical methods to evaluating its properties, including mean-field theory, linear response, and a primitive correlated model. The Hamiltonian can be compared to standard vibronic Hamiltonians, but is constructed without reference to potential energy surfaces, through direct differentiation of the one- and two-electron integrals at a single reference geometry. The nature of the model Hamiltonian in the harmonic and linear-coupling regime is investigated for pyrazine, where a simple time-dependent calculation including electron-vibration correlation is demonstrated to exhibit the well-studied population transfer between the S$_2$ and S$_1$ excited states.
