论文标题
关于定义明确的热相关函数在模拟振动光谱中的重要性
On the Importance of Well-Defined Thermal Correlation Functions in Simulating Vibronic Spectra
论文作者
论文摘要
讨论了与热振动相关函数的计算相关的两个困难。第一个是缺乏表达式表达式,在高温和$ t \至0 $ k限制下都是有效的。具体而言,如果分别考虑分区函数和传播器,则在极限$ t \至0 $ k中的热振动相关函数可能具有不确定的表格0/0。当分隔函数和传播器在谐波中均取消能量,从而允许在零点范围内共同考虑,该难度可以与偏差的旋转,从而可以与零点的启用,从而可以与零点的启用,从而可以与零点的启动,从而可以与零点的确定能量,从而允许在零体的范围内进行启动,从而可以与零体的启动,从而允许偏差。以$ t \至0 $ k的限制形式。第二个难度与振动相关函数的多相关性有关。我们从数值上表明,分支的选择不当会导致计算的相关函数和不正确的振动光谱中的不连续性。我们提出了一个相位跟踪过程,以确保相关函数的真实部分和虚构部分的连续性以恢复正确的光谱。我们通过模拟五苯在4 K和298 K的苯甲苯苯乙烯的UV-VIS吸收光谱来支持我们的发现。发现两者都与其实验性对应物非常吻合。
Two difficulties associated with the computations of thermal vibrational correlation functions are discussed. The first one is the lack of a well-behaved expression that is valid at both high-temperature and $T \to 0$ K limits. Specifically, if the partition function and the propagator are considered separately, then thermal vibrational correlation functions may have an indeterminate form 0/0 in the limit $T \to 0$ K. This difficulty is resolved when the partition function and the propagator are jointly considered in the harmonic approximation, which allows a problematic term that emanates from the zero-point energy to be cancelled out thereby producing a thermal correlation function with a determinate form in $T \to 0$ K limit. The second difficulty is related to the multivaluedness of the vibrational correlation function. We show numerically that an improper selection of branch leads to discontinuities in the computed correlation function and an incorrect vibronic spectra. We propose a phase tracking procedure that ensures continuity of both real and imaginary parts of the correlation function to recover the correct spectra. We support our findings by simulating the UV-vis absorption spectra of pentacene at 4 K and benzene at 298 K. Both are found to be in good agreement with their experimental counterparts.