论文标题

四部分完整构型相互作用量子蒙特卡洛用于相对论相关电子问题

Four-component Full Configuration Interaction Quantum Monte Carlo for Relativistic Correlated Electron Problems

论文作者

Anderson, Robert J., Booth, George H.

论文摘要

提出了完整构型相互作用量子蒙特卡洛(FCIQMC)方法的适应,用于包含沉重元素的相关电子问题和存在显着的相对论效应。修改后的算法允许在相对论的非对近似值中对Dirac--Coulomb(-Breit)Hamiltonian的四组分旋转器进行采样。旋转对称性的丧失和对复杂值的哈密顿矩阵元素的一般要求是将FCIQMC范围扩展到相对论领域的最直接考虑,并且有效实施的替代方案是动机和证明的。对于hydride的规范相关的四组分化学基准应用应用,我们表明,必要的修改并不特别不利地影响系统的(启动器)误差与FCIQMC计算的确切相关能量的收敛性,这主要由波浪函数的漏气所决定的,从而使计算上的努力构成了某种程度的验证,从而在某些方面遇到了某些问题。我们将该方法应用于氧化锡锡的光谱常数的更大问题,与122个Kramers生育旋转器中的28个电子相关联,与实验和先前的理论相对论研究发现了良好的一致性。

An adaptation of the full configuration interaction quantum Monte Carlo (FCIQMC) method is presented, for correlated electron problems containing heavy elements and the presence of significant relativistic effects. The modified algorithm allows for the sampling of the four-component spinors of the Dirac--Coulomb(--Breit) Hamiltonian within the relativistic no-pair approximation. The loss of spin symmetry and the general requirement for complex-valued Hamiltonian matrix elements are the most immediate considerations in expanding the scope of FCIQMC into the relativistic domain, and the alternatives for their efficient implementation are motivated and demonstrated. For the canonical correlated four-component chemical benchmark application of Thallium Hydride, we show that the necessary modifications do not particularly adversely affect the convergence of the systematic (initiator) error to the exact correlation energy for FCIQMC calculations, which is primarily dictated by the sparsity of the wave function, allowing the computational effort to somewhat bypass the formal increases in Hilbert space dimension for these problems. We apply the method to the larger problem of the spectroscopic constants of Tin Oxide, correlating 28 electrons in 122 Kramers-paired spinors, finding good agreement with experimental and prior theoretical relativistic studies.

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