Electronic flux densities in vibrating H2+in terms of vibronic eigenstates
Electronic flux densities in vibrating H2+in terms of vibronic eigenstates
复制标题
振动 H2 中的电子通量密度（以振动本征态表示）
DOI：
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发表时间：
2013
期刊：
影响因子：
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通讯作者：
J. F. Pérez
中科院分区：
文献类型：
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作者：
J. F. Pérez
分子系统的电子基态是一个挑战，因为在玻恩-奥本海默近似 (BOA) 中描述状态的习惯做法给出了真实的电子波函数，而 EFD 消失了 [1]。在这里，我们根据[2]的完整哈密顿量的精确振动能量本征态来解决问题。总波函数表示为 的线性组合，用于计算精确的 EFD，并将其与 BOA 框架内按比例耦合通道 (SCCh) 方法计算的近似 EFD 进行比较 [3]。对转折点附近的通量密度的分析表明，与电子波包（1 fs）相比，核波包需要更长的时间（1.4 fs）来改变其方向。另一方面，对高激发稳态的分析（不包括在 EFD 的计算中）表明可能会出现共振态，这可能是由于电子和核运动之间的相关性，即由于非绝热效应。此功能要求研究能量高于解离阈值的非玻恩-奥本海默态。
electronic ground state of a molecular system is a challenge, because the customary practice of describing the state in the Born–Oppenheimer approximation (BOA) gives real electronic wave function, for which the EFD vanishes [1]. Here we solve the problem in terms of accurate vibronic energy eigenstates of the complete Hamiltonian of [2]. The total wave function, expressed as a linear combination of the is used to compute an accurate EFD, which is compared with approximate EFD computed by scaled coupled–channels (SCCh) approach within the framework of the BOA [3]. Analysis of the flux densities close to the turning points shows that the nuclear wave packet takes longer time (1.4 fs) to change its direction compared to the electronic one (1 fs). On the other hand, analysis of the highly excited stationary states (not included for the computation of the EFD) suggests that resonant states can appear, presumably due to the correlation between the electronic and nuclear motion, i.e., due to non adiabatic effects. This feature calls for investigation of the non Born-Oppenheimer states with energies above the dissociation threshold.