Resonating valence bond wave function with molecular orbitals: application to first-row molecules.
Resonating valence bond wave function with molecular orbitals: application to first-row molecules.
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与分子轨道共振价键波函数：应用于第一行分子。
DOI：
10.1063/1.3249966
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发表时间：
2009
期刊：
影响因子：
--
通讯作者：
S. Sorella
中科院分区：
文献类型：
--
作者：
M. Marchi;Sam Azadi;M. Casula;S. Sorella
我们介绍了一种精确的量子化学计算的基础上，一个简单的变分波函数，定义为一个单一的双子，所有的电子耦合成单线对，结合一个真实的空间相关因子。该方法使用了约束变分优化，基于分子轨道的孪晶的扩展。它表明，最相关的非动力学相关性被正确地再现，一旦被认为是一个适当的分子轨道数n。n的值是通过要求在原子化极限下，原子由Hartree-Fock斯莱特行列式和Jastrow关联描述来确定的。的能量，以及其他物理和化学性质，然后给出了一个有效的变分方法的基础上，标准的量子蒙特卡罗技术。我们测试了一组homonases（Be（2），B（2），C（2），N（2），O（2），和F（2））和heteronases（LiF和CN）的二聚体，其中强非动力学相关和/或弱货车德瓦尔斯相互作用。
We introduce a method for accurate quantum chemical calculations based on a simple variational wave function, defined by a single geminal that couples all the electrons into singlet pairs, combined with a real space correlation factor. The method uses a constrained variational optimization, based on an expansion of the geminal in terms of molecular orbitals. It is shown that the most relevant nondynamical correlations are correctly reproduced once an appropriate number n of molecular orbitals is considered. The value of n is determined by requiring that, in the atomization limit, the atoms are described by Hartree-Fock Slater determinants with Jastrow correlations. The energetics, as well as other physical and chemical properties, are then given by an efficient variational approach based on standard quantum Monte Carlo techniques. We test this method on a set of homonuclear (Be(2), B(2), C(2), N(2), O(2), and F(2)) and heteronuclear (LiF and CN) dimers for which strong nondynamical correlations and/or weak van der Waals interactions are present.