Multicomponent Orbital-Optimized Perturbation Theory Methods: Approaching Coupled Cluster Accuracy at Lower Cost.
Multicomponent Orbital-Optimized Perturbation Theory Methods: Approaching Coupled Cluster Accuracy at Lower Cost.
复制标题
多分量轨道优化扰动理论方法：以较低成本接近耦合簇精度。
DOI：
--
复制
发表时间：
2020
影响因子：
5.7
通讯作者：
S. Hammes‐Schiffer
中科院分区：
文献类型：
--
作者：
Fabijan Pavošević;Benjamin J G Rousseau;S. Hammes‐Schiffer
多组分量子化学方法，如核电子轨道（NEO）方法，允许对电子和原子核进行一致的量子力学处理。由于轨道弛豫效应的重要性，发展计算上实用、精确和鲁棒的多分量波函数方法是具有挑战性的。本文发展了变分轨道优化的耦合团簇双方法（NEO-OOCCD）和轨道优化的二阶Møller-Plesset微扰理论方法（NEO-OOMP 2），并将其应用于一个质子和所有电子都被量子力学处理的分子体系。结果突出了轨道弛豫在多分量波函数方法中的重要性。NEO-SOS '-OOMP 2方法对电子-质子相关能以及电子相关能中的反自旋和同自旋分量进行了换算，发现它在质子密度、质子亲合能和优化几何结构方面的准确度几乎与NEO-OOCCD方法相同。NEO-SOS '-OOMP 2方法的一个优点是它可以用N4缩放来实现，其中N是系统大小的度量。这种方法将使未来的多组分波函数计算的结构，能量，反应路径，和动力学大大更大的化学系统。
Multicomponent quantum chemistry methods such as the nuclear-electronic orbital (NEO) method allow the consistent quantum mechanical treatment of electrons and nuclei. The development of computationally practical, accurate, and robust multicomponent wave function methods is challenging because of the importance of orbital relaxation effects. Herein the variational orbital-optimized coupled cluster with doubles method (NEO-OOCCD) and the orbital-optimized second-order Møller-Plesset perturbation theory method (NEO-OOMP2) with scaled-opposite-spin (SOS) versions are developed and applied to molecular systems in which a proton and all electrons are treated quantum mechanically. The results highlight the importance of orbital relaxation in multicomponent wave function methods. The NEO-SOS'-OOMP2 method, which scales the electron-proton correlation energy as well as the opposite-spin and same-spin components of the electronic correlation energy, is found to achieve nearly the same level of accuracy as the NEO-OOCCD method for proton densities, proton affinities, and optimized geometries. An advantage of the NEO-SOS'-OOMP2 method is that it can be implemented with N4 scaling, where N is a measure of the system size. This method will enable future multicomponent wave function calculations of structures, energies, reaction paths, and dynamics for substantially larger chemical systems.
影响因子：
5.5
作者：
Parrish RM;Burns LA;Smith DGA;Simmonett AC;DePrince AE 3rd;Hohenstein EG;Bozkaya U;Sokolov AY;Di Remigio R;Richard RM;Gonthier JF;James AM;McAlexander HR;Kumar A;Saitow M;Wang X;Pritchard BP;Verma P;Schaefer HF 3rd;Patkowski K;King RA;Valeev EF;Evangelista FA;Turney JM;Crawford TD;Sherrill CD
通讯作者：
Sherrill CD