NO2时域动力学中的慢周期振荡
Slow periodic oscillations in time domain dynamics of NO2
摘要：
通过在激发态上发射波包，研究了NO2分子在X2 A1和A2 B2电子态上的时域非绝热动力学，重点研究了迄今为止尚未引起人们关注的长时间（t>200 fs）的演化.我们发现，最初的快速扩展的波包，其次是在所有的能量缓慢周期性的分子内振动能量重新分配（IVER）的周期范围在0.3至几十ps。这些能量转移导致每个电子态的布居中具有相同周期的振荡。波包的传播表明，IVER频率也支配自相关函数的平方模的波动，|A（吨）|^2，在能量不高于圆锥交叉点底部太高的地方，但在更高的能量下不再是这种情况。例如，对于由基态电子表面的振动基态的几乎垂直激发制备的初始波包，|A（吨）|^2基本上反映了在受激电子态中弯曲频率和对称伸缩频率之间的1：2共振的失谐。这些理论结果被用来讨论最近在NO2的时域实验光谱中观察到的低频振荡的可能来源。
英文摘要：
We investigated the time domain nonadiabatic dynamics of NO2 on the coupled X2A1 and A2B2 electronic states by launching wave packets on the excited electronic state and focused on the evolution at long times (t>200 fs), which has received little attention up to now. We showed that the initial fast spreading of the wave packets is followed at all energies by slow periodic intramolecular vibronic energy redistribution (IVER) with periods in the range 0.3 to several tens of ps. These energy transfers lead to oscillations with the same periods in the population of each electronic state. Propagation of wave packets indicates that IVER frequencies also dominate the fluctuations of the squared modulus of the autocorrelation function, |A(t)|^2, at energies not too high above the bottom of the conical intersection, but that this is no longer the case at higher energies. For example, for initial wave packets prepared by almost vertical excitation of the vibrational ground state of the ground electronic surface, the oscillations of |A(t)|^2 essentially reflect the detuning from 1:2 resonance between the frequency of the bend and that of the symmetric stretch in the excited electronic state. These theoretical results were used to discuss the possible origin of the low frequency oscillations which were recently observed in time domain experimental spectra of NO2.
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