Charge Migration in HCCI Cations Probed by Strong Field Ionization: Time-Dependent Configuration Interaction and Vibrational Wavepacket Simulations
Charge Migration in HCCI Cations Probed by Strong Field Ionization: Time-Dependent Configuration Interaction and Vibrational Wavepacket Simulations
复制标题
强场电离探测 HCCI 阳离子中的电荷迁移：瞬态构型相互作用和振动波包模拟
DOI：
10.1021/acs.jpca.3c02667
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Schlegel, H. Bernhard
中科院分区：
文献类型：
--
作者：
Schlegel, H. Bernhard
中性碘乙炔的强场电离可以产生X和A离子的共格叠加，导致CCπ轨道和碘π类型孤子对之间的电荷迁移。这种电荷迁移导致阳离子到阳离子的强场电离速率的振荡，这可以用几个周期的强探测脉冲来监测。用含时组态相互作用(TDCI)模拟了HcCI+的X态和A态相干叠加的动力学和强场电离。当原子核被允许运动时，电子波函数需要乘以振动波函数。原子核运动是由振动包在阳离子X和A态势能面上的二次近似来模拟的。振动波包的重叠大约在10-15飞秒内衰减。因此，强场电离中的振荡在相同的时间尺度上衰减。在60-110飞秒处，强场电离的振动重叠和振荡中出现了复活。TDCi模拟表明，强场电离可以监测电荷迁移的衰变和恢复过程，强场电离具有2和4个周期的强线极化800 nm脉冲。7个周期的脉冲也可以看到复苏。
Strong field ionization of neutral iodoacetylene (HCCI) can produce a coherent superposition of the X and A cations and results in charge migration between the CC π orbital and the iodine π-type lone pair. This charge migration causes oscillations in the rate of strong field ionization of the cation to the dication that can be monitored using intense few-cycle probe pulses. The dynamics and strong field ionization of the coherent superposition the X and A states of HCCI+have been modeled by time-dependent configuration interaction (TDCI) simulations. When the nuclei are allowed to move, the electronic wavefunctions need to be multiplied by vibrational wavefunctions. Nuclear motion has been modeled by vibrational packets moving on quadratic approximations to the potential energy surfaces for the X and A states of the cation. The overlap of the vibrational wavepackets decays in about 10–15 fs. Consequently, the oscillations in the strong field ionization decay on the same time scale. A revival of the vibrational overlap and in the oscillations of the strong field ionization is seen at 60–110 fs. TDCI simulations show that the decay and revival of the charge migration can be monitored by strong field ionization with intense 2- and 4-cycle linearly polarized 800 nm pulses. The revival is also seen with 7-cycle pulses.