吡嗪分子多维振动动力学中Non-Condon效应

Non-Condon effect on multidimensional vibrational dynamics of pyrazine

采用优化控制理论和多组态含时Hartree结合的方法,研究了吡嗪分子在3个电子能级之间振动耦合模型中Non-Condon效应的影响;在非绝热近似下给出了跃迁偶极函数的具体形式,成功实现了Non-Condon效应下对吡嗪分子的飞秒激光控制;给出了不同初始能量下飞秒激光的优化图形,得到了整个电子态的布居和相应的优化激光脉冲形状。同Condon近似下的结果进行比较发现:跃迁偶极矩的不同方向对电子波函数的影响较大,相应的优化激光场的振荡周期也发生了改变。

Non-Condon effect on the three lowest singlet states vibronic coupling model of pyrazine was calculated using a com-bined approach of optimal control theory（OCT） and the multi-configuration time-dependent Hartree （MCTDH） method. Transi-tion-dipole-moment functions in the diabatic representation are presented. Different control tasks under Non-Condon effect were done using femtosecond laser pulse. The overall electronic state populations and corresponding optimal pulse are given with differ-ent initial guess energies. Compared with condon approximation calculation, the transition moment in different directions has sig-nificant effect on electronic wave functions, and the corresponding optimization of the oscillation period of the laser field has changed.