Analytical gradients of variational reduced-density-matrix and wavefunction-based methods from an overlap-reweighted semidefinite program.
Analytical gradients of variational reduced-density-matrix and wavefunction-based methods from an overlap-reweighted semidefinite program.
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来自重叠重加权半定程序的变分约化密度矩阵和基于波函数的方法的解析梯度。
DOI：
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发表时间：
2018
影响因子：
4.4
通讯作者：
D. Mazziotti
中科院分区：
文献类型：
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作者：
A. W. Schlimgen;D. Mazziotti
通过对原子轨道约化密度矩阵的变换，消除了N表示条件对轨道重叠矩阵的依赖，得到了变分双电子约化密度矩阵(2-RDM)方法的解析梯度。该变换通过双重叠矩阵的Cholesky分解来执行，生成了仅依赖于变换的约化哈密顿矩阵的导数的梯度的类似Hellmann-Feynman的表达式。该公式不仅适用于变分2-RDM方法，而且适用于全组态相互作用和完全活动空间自洽场等变分波函数方法。为了说明这一点，我们应用解析梯度对几种过渡金属络合物，八面体和三方柱状的CrF6，以及(乙烯-1，2-二硫代)镍或镍(EDT)_2的络合物进行了几何优化。
Analytical gradients of variational two-electron reduced-density matrix (2-RDM) methods are derived by transforming the atomic-orbital reduced-density matrices to remove the dependence of the N-representability conditions on the orbital-overlap matrix. The transformation, performed through a Cholesky decomposition of the geminal-overlap matrix, generates a Hellmann-Feynman-like expression for the gradient that only depends on the derivative of the transformed reduced Hamiltonian matrix. The formulation is applicable not only to the variational 2-RDM method but also to variational wavefunction methods like the full configuration interaction and complete active-space self-consistent-field. To illustrate, we apply the analytical gradients to perform geometry optimizations on several transition metal complexes, octahedral and trigonal prismatic CrF6 as well as the (ethylene-1,2-dithiolato)nickel, or Ni(edt)2, complex.
影响因子：
4.6
作者：
T. Schlöder;F. Brosi;B. J. Freyh;T. Vent-Schmidt;S. Riedel
通讯作者：
S. Riedel