Normal-ordered second-quantized Hamiltonian for molecular vibrations.
Normal-ordered second-quantized Hamiltonian for molecular vibrations.
复制标题
分子振动的正序第二量子化哈密顿量。
DOI：
10.1063/1.4901061
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发表时间：
2014
期刊：
影响因子：
--
通讯作者：
M. Hermes
中科院分区：
文献类型：
--
作者：
S. Hirata;M. Hermes
一个正常有序的第二量子化形式的哈密顿量推导出量子动力学在一个束缚势能面表示为泰勒级数在一个任意的正交，离域坐标集中在一个任意的几何形状。恒定的，第一，和第二阶激发振幅的哈密顿量被确定为基态能量，梯度和频率，分别的尺寸扩展的振动自洽场（XVSCF）方法或自洽声子方法。它们显示了V（1-n/2）的明确定义的尺寸依赖性，其中V是体积，n是与振幅相关的坐标数。它被用来快速推导出XVSCF方程和振动多体微扰方法与Møller-Plesset分割的哈密顿量。
A normal-ordered second-quantized form of the Hamiltonian is derived for quantum dynamics in a bound potential energy surface expressed as a Taylor series in an arbitrary set of orthogonal, delocalized coordinates centered at an arbitrary geometry. The constant, first-, and second-order excitation amplitudes of this Hamiltonian are identified as the ground-state energy, gradients, and frequencies, respectively, of the size-extensive vibrational self-consistent field (XVSCF) method or the self-consistent phonon method. They display the well-defined size dependence of V(1-n/2), where V is the volume and n is the number of coordinates associated with the amplitudes. It is used to rapidly derive the equations of XVSCF and vibrational many-body perturbation methods with the Møller-Plesset partitioning of the Hamiltonian.