Yao Y X, Liu J, Liu C, Lu W C, Wang C Z, Ho K M
Ames Laboratory-US DOE and Department of Physics and Astronomy, Iowa State University, Ames, Iowa 50011, USA.
State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun, Jilin 130021, China.
Sci Rep. 2015 Aug 28;5:13478. doi: 10.1038/srep13478.
We present an efficient method for calculating the electronic structure and total energy of strongly correlated electron systems. The method extends the traditional Gutzwiller approximation for one-particle operators to the evaluation of the expectation values of two particle operators in the many-electron Hamiltonian. The method is free of adjustable Coulomb parameters, and has no double counting issues in the calculation of total energy, and has the correct atomic limit. We demonstrate that the method describes well the bonding and dissociation behaviors of the hydrogen and nitrogen clusters, as well as the ammonia composed of hydrogen and nitrogen atoms. We also show that the method can satisfactorily tackle great challenging problems faced by the density functional theory recently discussed in the literature. The computational workload of our method is similar to the Hartree-Fock approach while the results are comparable to high-level quantum chemistry calculations.
我们提出了一种计算强关联电子系统的电子结构和总能量的有效方法。该方法将单粒子算符的传统古兹维勒近似扩展到多电子哈密顿量中双粒子算符期望值的计算。该方法无需可调库仑参数，在总能量计算中不存在双重计数问题，并且具有正确的原子极限。我们证明该方法能很好地描述氢和氮团簇以及由氢和氮原子组成的氨的键合和解离行为。我们还表明该方法能够令人满意地解决文献中最近讨论的密度泛函理论所面临的巨大挑战问题。我们方法的计算工作量与哈特里 - 福克方法相似，而结果可与高水平量子化学计算相媲美。
