Odbadrakh Tuguldur T, Jordan Kenneth D
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
J Chem Phys. 2016 Jan 21;144(3):034111. doi: 10.1063/1.4940217.
We present the dispersion-induced dipole moments of coupled Drude oscillators obtained from two approaches. The first approach evaluates the dipole moment using the second-order Rayleigh-Schrödinger perturbation theory wave function allowing for dipole-dipole and dipole-quadrupole coupling. The second approach, based on response theory, employs an integral of the dipole-dipole polarizability of one oscillator and the dipole-dipole-quadrupole hyperpolarizability of the other oscillator over imaginary frequencies. The resulting dispersion dipoles exhibit an R(-7) dependence on the separation between the two oscillators and are connected to the leading-order C6/R(6) dispersion energy through the electrostatic Hellmann-Feynman theorem.
我们展示了通过两种方法获得的耦合德鲁德振子的色散诱导偶极矩。第一种方法使用二阶瑞利 - 薛定谔微扰理论波函数来评估偶极矩,该波函数考虑了偶极 - 偶极和偶极 - 四极耦合。第二种方法基于响应理论,利用一个振子的偶极 - 偶极极化率与另一个振子的偶极 - 偶极 - 四极超极化率在虚频率上的积分。所得的色散偶极矩表现出与两个振子之间距离的R(-7)依赖性,并通过静电赫尔曼 - 费曼定理与主导阶C6/R(6)色散能相关联。