A tractable and accurate electronic structure method for static correlations: the perfect hextuples model

The Journal of Chemical Physics
John A Parkhill, Martin Head-Gordon

Abstract

We present the next stage in a hierarchy of local approximations to complete active space self-consistent field (CASSCF) model in an active space of one active orbital per active electron based on the valence orbital-optimized coupled-cluster (VOO-CC) formalism. Following the perfect pairing (PP) model, which is exact for a single electron pair and extensive, and the perfect quadruples (PQ) model, which is exact for two pairs, we introduce the perfect hextuples (PH) model, which is exact for three pairs. PH is an approximation to the VOO-CC method truncated at hextuples containing all correlations between three electron pairs. While VOO-CCDTQ56 requires computational effort scaling with the 14th power of molecular size, PH requires only sixth power effort. Our implementation also introduces some techniques which reduce the scaling to fifth order and has been applied to active spaces roughly twice the size of the CASSCF limit without any symmetry. Because PH explicitly correlates up to six electrons at a time, it can faithfully model the static correlations of molecules with up to triple bonds in a size-consistent fashion and for organic reactions usually reproduces CASSCF with chemical accuracy. The convergence of the PP, PQ, a...Continue Reading

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Citations

Feb 11, 2012·The Journal of Chemical Physics·James B Robinson, Peter J Knowles
Sep 25, 2012·The Journal of Chemical Physics·David W Small, Martin Head-Gordon
Aug 24, 2013·The Journal of Chemical Physics·Stephan N Steinmann, Weitao Yang
Jan 17, 2015·The Journal of Chemical Physics·David W SmallMartin Head-Gordon
Oct 10, 2014·The Journal of Chemical Physics·Nicholas J Mayhall, Martin Head-Gordon
Aug 13, 2015·The Journal of Physical Chemistry Letters·Yong-Hui TianJingsong Huang
Jan 10, 2012·Chemical Reviews·Dmitry I LyakhRodney J Bartlett
Jan 25, 2017·Journal of Chemical Theory and Computation·Samuel ManzerMartin Head-Gordon
Sep 19, 2014·Physical Chemistry Chemical Physics : PCCP·Nicholas J MayhallMartin Head-Gordon
Mar 4, 2020·Journal of Computational Chemistry·Lu T XuThom H Dunning
Nov 22, 2012·Physical Chemistry Chemical Physics : PCCP·Franziska BellMartin Head-Gordon
Aug 24, 2017·The Journal of Chemical Physics·Chenyang LiFrancesco A Evangelista
Jul 25, 2018·The Journal of Chemical Physics·Francesco A Evangelista
Mar 19, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Susi LehtolaChristian Van Alsenoy
Mar 21, 2019·Annual Review of Physical Chemistry·Chenyang Li, Francesco A Evangelista
Nov 23, 2017·The Journal of Chemical Physics·Paul M Zimmerman
Aug 14, 2012·Journal of Chemical Theory and Computation·James B Robinson, Peter J Knowles

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Software Mentioned

MP2
PQ
CCD
VOO
CC
CASSCF
CCDTQ
BLAS
OO
QCHEM

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