Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, USA.
J Chem Phys. 2011 Mar 7;134(9):094115. doi: 10.1063/1.3556707.
We investigate the dynamical mean-field theory (DMFT) from a quantum chemical perspective. Dynamical mean-field theory offers a formalism to extend quantum chemical methods for finite systems to infinite periodic problems within a local correlation approximation. In addition, quantum chemical techniques can be used to construct new ab initio Hamiltonians and impurity solvers for DMFT. Here, we explore some ways in which these things may be achieved. First, we present an informal overview of dynamical mean-field theory to connect to quantum chemical language. Next, we describe an implementation of dynamical mean-field theory where we start from an ab initio Hartree-Fock Hamiltonian that avoids double counting issues present in many applications of DMFT. We then explore the use of the configuration interaction hierarchy in DMFT as an approximate solver for the impurity problem. We also investigate some numerical issues of convergence within DMFT. Our studies are carried out in the context of the cubic hydrogen model, a simple but challenging test for correlation methods. Finally, we finish with some conclusions for future directions.
我们从量子化学的角度研究了动力学平均场理论（DMFT）。动力学平均场理论提供了一种形式体系，可以将量子化学方法从有限系统扩展到局部相关近似下的无限周期性问题。此外，量子化学技术可用于为 DMFT 构建新的从头算哈密顿量和杂质求解器。在这里，我们探索了实现这些目标的一些方法。首先，我们提供了一个关于动力学平均场理论的非正式概述，以便与量子化学语言联系起来。接下来，我们描述了一个动力学平均场理论的实现，其中我们从避免 DMFT 许多应用中存在的双重计数问题的从头算 Hartree-Fock 哈密顿量开始。然后，我们探讨了在 DMFT 中使用组态相互作用层次结构作为杂质问题的近似求解器的方法。我们还研究了 DMFT 中收敛的一些数值问题。我们的研究是在立方氢模型的背景下进行的，这是对相关方法的一个简单但具有挑战性的测试。最后，我们对未来的方向进行了总结。
