Stoychev Georgi L, Auer Alexander A, Gauss Jürgen, Neese Frank
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany.
Department Chemie, Johannes Gutenberg-Universität Mainz, Duesbergweg 10-14, 55128 Mainz, Germany.
J Chem Phys. 2021 Apr 28;154(16):164110. doi: 10.1063/5.0047125.
We present a derivation and efficient implementation of the formally complete analytic second derivatives for the domain-based local pair natural orbital second order Møller-Plesset perturbation theory (MP2) method, applicable to electric or magnetic field-response properties but not yet to harmonic frequencies. We also discuss the occurrence and avoidance of numerical instability issues related to singular linear equation systems and near linear dependences in the projected atomic orbital domains. A series of benchmark calculations on medium-sized systems is performed to assess the effect of the local approximation on calculated nuclear magnetic resonance shieldings and the static dipole polarizabilities. Relative deviations from the resolution of the identity-based MP2 (RI-MP2) reference for both properties are below 0.5% with the default truncation thresholds. For large systems, our implementation achieves quadratic effective scaling, is more efficient than RI-MP2 starting at 280 correlated electrons, and is never more than 5-20 times slower than the equivalent Hartree-Fock property calculation. The largest calculation performed here was on the vancomycin molecule with 176 atoms, 542 correlated electrons, and 4700 basis functions and took 3.3 days on 12 central processing unit cores.
我们给出了基于域的局部对自然轨道二阶莫勒-普列斯特定则微扰理论（MP2）方法形式上完整的解析二阶导数的推导和高效实现，该方法适用于电场或磁场响应性质，但不适用于谐波频率。我们还讨论了与奇异线性方程组以及投影原子轨道域中的近线性相关性相关的数值不稳定性问题的出现和避免。对中型系统进行了一系列基准计算，以评估局部近似对计算的核磁共振屏蔽和静态偶极极化率的影响。在默认截断阈值下，这两种性质与基于单位分解的MP2（RI-MP2）参考值的相对偏差均低于0.5%。对于大型系统，我们的实现实现了二次有效缩放，从280个相关电子开始比RI-MP2更高效，并且比等效的哈特里-福克性质计算慢不超过5至20倍。这里进行的最大计算是针对具有176个原子、542个相关电子和4700个基函数的万古霉素分子，在12个中央处理器核心上花费了3.3天时间。
