Projected seniority-two orbital optimization of the antisymmetric product of one-reference orbital geminal
Projected seniority-two orbital optimization of the antisymmetric product of one-reference orbital geminal
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DOI：
10.1063/1.4880820
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发表时间：
2014-06-07
影响因子：
4.4
通讯作者：
Van Neck, Dimitri
中科院分区：
文献类型：
--
作者：
Boguslawski, Katharina;Tecmer, Pawel;Van Neck, Dimitri
我们提出了一个新的，非变分轨道优化方案的反对称产品的单参考轨道双子波函数。我们的方法的动机是观察到，轨道优化的资深零配置相互作用（CI）展开产生类似的结果，轨道优化的资深零加2 CI展开[L. Bytautas，T. M.亨德森角A. Jimenez-Hoyos，J. K. Ellis和G. E. Scuseria，J.Chem.Phys.135，044119（2011）]。的C-2和LiF分子进行数值分析，为CH 2单线态双自由基以及对称拉伸的假设（线性）氢链。对于这些测试情况下，所提出的轨道优化协议产生类似的结果，其变分轨道优化对应，但在大多数情况下，防止破坏分子轨道。(C)2014 AIP Publishing LLC.
We present a new, non-variational orbital-optimization scheme for the antisymmetric product of one-reference orbital geminal wave function. Our approach is motivated by the observation that an orbital-optimized seniority-zero configuration interaction (CI) expansion yields similar results to an orbital-optimized seniority-zero-plus-two CI expansion [L. Bytautas, T. M. Henderson, C. A. Jimenez-Hoyos, J. K. Ellis, and G. E. Scuseria, J. Chem. Phys. 135, 044119 (2011)]. A numerical analysis is performed for the C-2 and LiF molecules, for the CH2 singlet diradical as well as for the symmetric stretching of hypothetical (linear) hydrogen chains. For these test cases, the proposed orbital-optimization protocol yields similar results to its variational orbital optimization counterpart, but prevents symmetry-breaking of molecular orbitals in most cases. (C) 2014 AIP Publishing LLC.