A unified scheme for ab initio molecular orbital theory and path integral molecular dynamics
A unified scheme for ab initio molecular orbital theory and path integral molecular dynamics
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DOI：
10.1063/1.1407289
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发表时间：
2001-11-22
影响因子：
4.4
通讯作者：
Miura, S
中科院分区：
文献类型：
--
作者：
Shiga, M;Tachikawa, M;Miura, S
我们提出了一种精确计算化学物质的一般方法，它以量子力学的方式处理原子核和电子，采用从头算分子轨道理论计算电子结构，采用路径积分分子动力学计算原子核。本方法使物理量的评估依赖于核配置以及电子结构，玻恩-奥本海默绝热近似的框架内。作为应用，我们给出了电响应性质--偶极矩和极化率的路径积分公式，它表征了在一定温度下，当存在均匀静电场时，电子结构和核构型的变化。我们还演示了使用本方法计算水分子和温度和同位素效应的结果进行了讨论。(C)2001年美国物理学会。
We present a general approach for accurate calculation of chemical substances which treats both nuclei and electrons quantum mechanically, adopting ab initio molecular orbital theory for the electronic structure and path integral molecular dynamics for the nuclei. The present approach enables the evaluation of physical quantities dependent on the nuclear configuration as well as the electronic structure, within the framework of Born-Oppenheimer adiabatic approximation. As an application, we give the path integral formulation of electric response properties-dipole moment and polarizability, which characterize the changes both in electronic structure and nuclear configuration at a given temperature when uniform electrostatic field is present. We also demonstrate the calculation of a water molecule using the present approach and the result of temperature and isotope effects is discussed. (C) 2001 American Institute of Physics.