振动跃迁剖面中非康登效应的累积展开快速估计
Cumulant expansion for fast estimate of non-Condon effects in vibronic transition profiles
摘要：
当存在时，累积量可以提供关于给定分布的有价值的信息，并且原则上可以用于完全重建或近似父分布函数。先前报道的用于Franck-Condon轮廓的累积扩展方法[Faraday Discuss.，150，363（2011）]扩展到也描述在Franck-Condon近似中弱允许或禁止的振动跃迁的轮廓（非Condon轮廓）。在谐波近似的累积量的振动光谱轮廓可以评估解析和数值与相干状态为基础的生成函数，占杜辛斯基效应。作为例证，本文在电偶极子和（线性）Herzberg-Teller近似下，给出了零开尔文和有限温度下苯的单光子$1 ^{1}\mathrm{A_{g}}\rightarrow1 ^{1}\mathrm{B_{2u}}$紫外吸收谱。
英文摘要：
When existing, cumulants can provide valuable information about a given distribution and can in principle be used to either fully reconstruct or approximate the parent distribution function. A previously reported cumulant expansion approach for Franck-Condon profiles [Faraday Discuss., 150, 363 (2011)] is extended to describe also the profiles of vibronic transitions that are weakly allowed or forbidden in the Franck-Condon approximation (non-Condon profiles). In the harmonic approximation the cumulants of the vibronic spectral profile can be evaluated analytically and numerically with a coherent state-based generating function that accounts for the Duschinsky effect. As illustration, the one-photon $1 ^{1}\mathrm{A_{g}}\rightarrow1 ^{1}\mathrm{B_{2u}}$ UV absorption spectrum of benzene in the electric dipole and (linear) Herzberg-Teller approximation is presented herein for zero Kelvin and finite temperatures.
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