期刊
JOURNAL OF CHEMICAL PHYSICS
卷 149, 期 24, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.5052667
关键词
-
资金
- Office of Science, Office of Basic Energy Sciences, U.S. Department of Energy [DE-AC02-05CH11231]
We report the failure of coupled-cluster valence-bond (CCVB) theory with two-pair configurations [D. W. Small and M. Head-Gordon, J. Chem. Phys. 130, 084103 (2009)] for open-shell (OS) spin-frustrated systems where including three-pair configurations is necessary to properly describe strong spin-correlations. We extend OS-CCVB by augmenting the model with three-pair configurations within the independent amplitude approximation. The resulting new electronic structure model, OS-CCVB+i3, involves only a quadratic number of independent wavefunction parameters. It includes the recently reported closed-shell CCVB+i3 as a special case. Its cost is dominated by integral transformations, and it is capable of breaking multiple bonds exactly for all systems examined so far. The strength of OS-CCVB+i3 is highlighted in realistic systems including the [CaMn3O4] cubane subunit of the oxygen-evolving complex and a molecular magnet with the [Cr-9] core unit as well as model systems such as N-3, V3O3, and P-5. We show that OS-CCVB+i3 is only slightly dependent on the underlying perfect-pairing reference, while OS-CCVB shows a stronger dependence. We also emphasize the compactness of the OS-CCVB+i3 wavefunction compared to the heat-bath configuration interaction wavefunction, a recently introduced soft exponential-scaling approach. Published by AIP Publishing.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据