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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Reduced and exact quantum dynamics of the vibrational relaxation of a molecular system interacting with a finite-dimensional bath
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Reduced and exact quantum dynamics of the vibrational relaxation of a molecular system interacting with a finite-dimensional bath

机译：与有限维浴相互作用的分子系统的振动弛豫的减小且精确的量子动力学

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摘要

We investigate the vibrational relaxation of a Morse oscillator, nonlinearly coupled to a finite-dimensional bath of harmonic oscillators at zero temperature, using two different approaches: Reduced dynamics with the help of the Lindblad formalism of reduced density matrix theory in combination with Fermi's Golden Rule, and exact dynamics (within the chosen model) with the multiconfiguration time-dependent Hartree (MCTDH) method. Two different models have been constructed, the situation where the bath spectrum is exactly resonant with the anharmonic oscillator transition frequencies, and the case for which the subsystem is slightly off-resonant with the environment. At short times, reduced dynamics calculations describe the relaxation process qualitatively well but fail to reproduce recurrences observed with MCTDH for longer times. Lifetimes of all the vibrational levels of the Morse oscillator have been calculated, and both Lindblad and MCTDH results show the same dependence of the lifetimes on the initial vibrational state quantum number. A prediction, which should be generic for adsorbate systems is a striking, sharp increase of lifetimes of the subsystem vibrational levels close to the dissociation limit. This is contradictory with harmonic/linear extrapolation laws, which predict a monotonic decrease of the lifetime with initial vibrational quantum number.
机译：我们使用两种不同的方法研究了在零温度下非线性耦合到谐振子的有限维浴的Morse振荡器的振动弛豫，它使用两种不同的方法：借助密度矩阵理论的Lindblad形式化理论和费米黄金定律相结合，降低了动力学，以及采用多配置时变哈特里（MCTDH）方法的精确动力学（在所选模型内）。已经构建了两种不同的模型，即浴频谱与非谐振荡器跃迁频率精确共振的情况，以及子系统与环境略有共振的情况。在较短的时间内，减少的动力学计算在质量上很好地描述了松弛过程，但无法重现使用MCTDH观察到的长时间重复。已经计算出了莫尔斯振荡器的所有振动能级的寿命，并且林德布拉德（Lindblad）和MCTDH结果都显示出寿命对初始振动态量子数的依赖性相同。对于吸附剂系统来说应该是通用的预测是子系统振动水平接近解离极限的寿命急剧增加。这与谐波/线性外推定律相矛盾，后者预测寿命随初始振动量子数而单调减少。

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