论文标题
量子化学中二十年的辅助场量子蒙特卡洛：主体化学和债券破裂的概述和评估
Twenty Years of Auxiliary-Field Quantum Monte Carlo in Quantum Chemistry: An Overview and Assessment on Main Group Chemistry and Bond-Breaking
论文作者
论文摘要
在这项工作中，我们从计算量子化学的角度介绍了无量辅助辅助场量子蒙特卡洛（PH-AFQMC）方法，并介绍了其在主要组化学和键合的问题上的数值评估，总计1004个相对能量。尽管我们的基准研究有限，但我们提出建议将pH-AFQMC用于一般主要组化学应用。对于单个决定性波函数在定性上精确的系统，我们期望pH-AFQMC的准确性与单个决定符试验波函数在与单打和双打（CCSD）（CCSD）（CCSD）（CCSD）（CCSD（CCSD）（CCSD（CCSD））之间（CCSD（CCSD））之间。对于这些应用程序，当规范CCSD（T）太昂贵而无法运行时，PH-AFQMC应该是一种选择。对于要进行定性准确性需要多引用（MR）波函数的系统，pH-AFQMC比MR扰动理论方法更准确，并且与MR构型相互作用（MRCI）方法具有竞争力。由于与MRCI相比，由于pH-AFQMC的计算效率，我们建议将pH-AFQMC作为处理MR问题中动态相关性的首选方法。最后，我们讨论了pH-AFQMC方法未来发展的重要方向。
In this work, we present an overview of the phaseless auxiliary-field quantum Monte Carlo (ph- AFQMC) approach from a computational quantum chemistry perspective, and present a numerical assessment of its performance on main group chemistry and bond-breaking problems with a total of 1004 relative energies. While our benchmark study is somewhat limited, we make recommendations for the use of ph-AFQMC for general main-group chemistry applications. For systems where single determinant wave functions are qualitatively accurate, we expect the accuracy of ph-AFQMC in conjunction with a single determinant trial wave function to be between that of coupled-cluster with singles and doubles (CCSD) and CCSD with perturbative triples (CCSD(T)). For these applications, ph-AFQMC should be a method of choice when canonical CCSD(T) is too expensive to run. For systems where multi-reference (MR) wave functions are needed for qualitative accuracy, ph-AFQMC is far more accurate than MR perturbation theory methods and competitive with MR configuration interaction (MRCI) methods. Due to the computational efficiency of ph-AFQMC compared to MRCI, we recommended ph-AFQMC as a method of choice for handling dynamic correlation in MR problems. We conclude with a discussion of important directions for future development of the ph-AFQMC approach.
