Newton–Raphson optimization of the many‐body nonadiabatic wave function expressed in terms of explicitly correlated Gaussian functions
Newton–Raphson optimization of the many‐body nonadiabatic wave function expressed in terms of explicitly correlated Gaussian functions
复制标题
用显式相关高斯函数表示的多体非绝热波函数的牛顿-拉夫森优化
DOI：
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发表时间：
1992
期刊：
影响因子：
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通讯作者：
L. Adamowicz
中科院分区：
文献类型：
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作者：
P. Kozlowski;L. Adamowicz
非绝热多体波函数用显式相关的高斯型基函数表示。对所有粒子(原子核和电子)的运动一视同仁，通过排列对称性区分粒子。用最近提出的方法在变分计算中确定了非绝热波函数[P.M.Kozlowski和L.Adamowicz，J.Chem]。太棒了。95,6681(1991)]。在这种方法中，不需要将质心运动与内部运动直接分离。描述了变分泛函关于高斯指数的一阶和二阶导数的解析理论及其与牛顿-拉夫森优化技术相结合的计算实现。最后给出了一些数值算例。
A nonadiabatic many‐body wave function is represented in terms of explicitly correlated Gaussian‐type basis functions. Motions of all particles (nuclei and electrons) are treated equally and particles are distinguished via permutational symmetry. The nonadiabatic wave function is determined in a variational calculation with the use of the method proposed recently [P. M. Kozlowski and L. Adamowicz, J. Chem. Phys. 95, 6681 (1991)]. In this approach no direct separation of the center‐of‐mass motion from the internal motion is required. The theory of analytical first and second derivatives of the variational functional with respect to the Gaussian exponents and its computational implementation in conjunction with the Newton–Raphson optimization technique is described. Finally, some numerical examples are shown.