Consistent treatment of quantum-mechanical and classical degrees of freedom in mixed quantum-classical simulations
Consistent treatment of quantum-mechanical and classical degrees of freedom in mixed quantum-classical simulations
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混合量子经典模拟中量子力学和经典自由度的一致处理
DOI：
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发表时间：
1998
期刊：
影响因子：
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通讯作者：
G. Stock
中科院分区：
文献类型：
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作者：
U. Müller;G. Stock
概述了非绝热分子过程的混合量子-经典公式。基于最近引入的映射形式[Stock and Thoss， Phys.]Rev. Lett. 78, 578(1997)]，该公式采用离散电子状态到连续变量的量子力学精确映射，从而通过连续变量描述电子和核自由度的动力学。结果表明，映射形式的经典评价结果是电子自由度和核自由度的自洽描述，它以完全等价的方式处理两种类型的动态变量。因此，该方法的适用性完全取决于经典近似的有效性，而不依赖于额外的假设，例如经典理论和量子力学理论的特别组合。零点能量在电子自由度中不受限制流动的观察表明了经典近似的局限性。H……
A mixed quantum-classical formulation of nonadiabatic molecular processes is outlined. Based on a recently introduced mapping formalism [Stock and Thoss, Phys. Rev. Lett. 78, 578 (1997)], the formulation employs a quantum-mechanically exact mapping of discrete electronic states onto continuous variables, thus describing the dynamics of both electronic and nuclear degrees of freedom by continuous variables. It is shown that the classical evaluation of the mapping formalism results in a self-consistent description of electronic and nuclear degrees of freedom, which treats both types of dynamical variables in a completely equivalent way. The applicability of the approach is thus solely determined by the validity of the classical approximation and does not rest on additional assumptions such as the ad hoc combination of classical and quantum-mechanical theories. The observation of unrestricted flow of zero-point energy in the electronic degrees of freedom indicates the limits of the classical approximation. H...