基于零温经典轨迹的多原子分子非零温振动电子光谱
Nonzero-temperature vibronic spectra of polyatomic molecules from a zero-temperature classical trajectory
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中文总结 AI 辅助
该研究结合相干热场动力学与单海森近似，开发出低成本的非零温振动电子光谱模拟方法，可高效计算多原子分子的相关光谱，在莫尔斯系统及实际分子体系中验证了方法的有效性。
中文摘要 AI 辅助
通过将相干热场动力学与单海森近似相结合，我们实现了弱非谐系统低至中等分辨率振动电子光谱的非零温模拟，其额外计算成本相对于零温计算可忽略不计。单海森相干热场高斯波包动力学在任意简谐势中是精确的，只要参考海森是最终势能面的海森。当应用于非谐性递增、温度变化的莫尔斯系统时，该方法成功捕捉到激发态非谐性和关键的温度依赖光谱特征，包括热带和谱线展宽。将该方法与从头算动力学相结合，我们通过计算萘、氨基香豆素C450和苯基自由基的吸收光谱，以及SeO₂⁻的光电子光谱，证明了其实用性。在从头算单海森近似下，零温光谱的计算成本为经典分子动力学（约数小时），而所有非零温光谱均可在数秒内完成计算。
英文摘要
By combining coherence thermofield dynamics with the single-Hessian approximation, we enable simulations of low- to medium-resolution vibronic spectra of weakly anharmonic systems at nonzero temperatures, at negligible additional cost relative to zero-temperature calculations. Single-Hessian coherence thermofield Gaussian wavepacket dynamics is exact in any harmonic potential, provided that the reference Hessian is that of the final surface. When applied to Morse systems of increasing anharmonicity and varying temperature, this method successfully captures excited-state anharmonicity and key temperature-dependent spectral features, including hot bands and broadening. By combining the method with on-the-fly ab initio dynamics, we demonstrate its utility by computing the absorption spectra of naphthalene, aminocoumarin C450, and phenyl radical, and the photoelectron spectrum of SeO$_{2}^{-}$ . Within the ab initio single-Hessian approximation, after the zero-temperature spectrum is obtained at the cost of classical molecular dynamics (on the order of hours), all nonzero-temperature spectra are computed in seconds.
