论文标题
超出kasha规则和振动光谱的光物理学的半经典方法超出了condon近似。矿物质的情况
Semiclassical Approach to Photophysics Beyond Kasha's Rule and Vibronic Spectroscopy Beyond the Condon Approximation. The Case of Azulene
论文作者
论文摘要
叠氮是一种原型分子,具有从第二个激发电子状态的异常荧光,因此违反了Kasha的规则,并且具有在Condon近似中无法理解的发射光谱。为了更好地理解叠氮和其他非惯性分子的光体物理学和光谱,我们开发了一种系统的,一般,有效的计算方法,将核的半经典动力学与从头开始的电子结构相结合。首先,为了分析非绝热效应,我们通过严格的绝热度量来补充标准人口动态,并用多表面脱落表示。其次,我们提出了一种新的半经典方法,用于模拟非核对光谱,该方法将延伸的融化高斯近似值与有效的单hessian方法结合在一起。 s $ _ {1} \ leftarrow $ s $ _0 $和s $ _ {2} \ leftarrow $ s $ _0 $吸收和s $ _ {2} \ rightArrow $ s $ s $ _0 $的股骨发射光谱,在新的实验中记录在我们计算的新实验中。我们发现评估光谱的准确性需要治疗非谐度,赫兹伯格(Herzberg) - 泰尔(Teller)和模式混合效应。
Azulene is a prototypical molecule with an anomalous fluorescence from the second excited electronic state, thus violating Kasha's rule, and with an emission spectrum that cannot be understood within the Condon approximation. To better understand photophysics and spectroscopy of azulene and other non-conventional molecules, we develop a systematic, general, and efficient computational approach combining semiclassical dynamics of nuclei with ab initio electronic structure. First, to analyze the nonadiabatic effects, we complement the standard population dynamics by a rigorous measure of adiabaticity, estimated with the multiple-surface dephasing representation. Second, we propose a new semiclassical method for simulating non-Condon spectra, which combines the extended thawed Gaussian approximation with the efficient single-Hessian approach. S$_{1} \leftarrow$ S$_0$ and S$_{2} \leftarrow$ S$_0$ absorption and S$_{2} \rightarrow$ S$_0$ emission spectra of azulene, recorded in a new set of experiments, agree very well with our calculations. We find that accuracy of the evaluated spectra requires the treatment of anharmonicity, Herzberg--Teller, and mode-mixing effects.