Quantum tunneling splittings from path-integral molecular dynamics.
Quantum tunneling splittings from path-integral molecular dynamics.
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DOI：
10.1063/1.4943867
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发表时间：
2016-03
期刊：
影响因子：
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通讯作者：
E. Mátyus;D. Wales;S. Althorpe
中科院分区：
文献类型：
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作者：
E. Mátyus;D. Wales;S. Althorpe
我们说明如何路径积分分子动力学可以用来计算分子或簇的基态隧道分裂。该方法通过隧道连通的退化井之间的密度矩阵元的比值得到分裂。我们提出了一个简单的热力学积分方案来评估这些元素。全维丙二醛屈服隧道裂缝的数值试验结果与扩散蒙特卡罗计算结果基本一致。
We illustrate how path-integral molecular dynamics can be used to calculate ground-state tunnelling splittings in molecules or clusters. The method obtains the splittings from ratios of density matrix elements between the degenerate wells connected by the tunnelling. We propose a simple thermodynamic integration scheme for evaluating these elements. Numerical tests on fully dimensional malonaldehyde yield tunnelling splittings in good overall agreement with the results of diffusion Monte Carlo calculations.