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Driven similarity renormalization group: Third-order multireference perturbation theory

机译:驱动相似性重整化组:三阶多重参考   微扰理论

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摘要

A third-order multireference perturbation theory based on the drivensimilarity renormalization group approach (DSRG-MRPT3) is presented. TheDSRG-MRPT3 method has several appealing features: a) it is intruder free, b) itis size consistent, c) it leads to a non-iterative algorithm with ${\calO}(N^6)$ scaling, and d) it includes reference relaxation effects. TheDSRG-MRPT3 scheme is benchmarked on the potential energy curves of F$_2$,H$_2$O$_2$, C$_2$H$_6$, and N$_2$ along the F-F, O-O, C-C, and N-N bonddissociation coordinates, respectively. The nonparallelism errors of DSRG-MRPT3are consistent to those of CASPT3 and MRCISD, and show significant improvementsover those obtained from DSRG second-order multireference perturbation theory.Our efficient implementation of the DSRG-MRPT3 based on factorized electronrepulsion integrals enables studies of medium-sized open-shell organiccompounds. This point is demonstrated with computations of the singlet-tripletsplitting ($\Delta_{\rm ST} = E_{\rm T} - E_{\rm S}$) of 9,10-anthracyne. Atthe DSRG-MRPT3 level of theory, our best estimate of the adiabatic $\Delta_{\rmST}$ is 3.9 kcal mol$^{-1}$, a value that is within 0.1 kcal mol$^{-1}$ frommultireference coupled cluster results.
机译:提出了基于驱动相似度归一化群方法(DSRG-MRPT3)的三阶多参考摄动理论。 DSRG-MRPT3方法具有几个吸引人的功能:a)无入侵者,b)大小一致,c)导致采用$ {\ calO}(N ^ 6)$缩放的非迭代算法,并且d)包括参考松弛效果。 DSRG-MRPT3方案的基准是沿着FF,OO,CC和NN的势能曲线F $ _2 $,H $ _2 $ O $ _2 $,C $ _2 $ H $ _6 $和N $ _2 $键解离坐标分别。 DSRG-MRPT3的非平行度误差与CASPT3和MRCISD一致,并且相对于从DSRG二阶多参考微扰理论获得的非平行度误差有显着改进。壳有机化合物。通过对9,10-蒽的单重态-三重态分裂($ \ Delta _ {\ rm ST} = E _ {\ rm T}-E _ {\ rm S} $)的计算证明了这一点。在DSRG-MRPT3的理论水平上,我们对绝热$ \ Delta _ {\ rmST} $的最佳估计为3.9 kcal mol $ ^ {-1} $,与多参考值相比,该值在0.1 kcal mol $ ^ {-1} $之内耦合聚类结果。

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