The limits of local correlation theory: electronic delocalization and chemically smooth potential energy surfaces

The Journal of Chemical Physics
Joseph E SubotnikMartin Head-Gordon

Abstract

Local coupled-cluster theory provides an algorithm for measuring electronic correlation quickly, using only the spatial locality of localized electronic orbitals. Previously, we showed [J. Subotnik et al., J. Chem. Phys. 125, 074116 (2006)] that one may construct a local coupled-cluster singles-doubles theory which (i) yields smooth potential energy surfaces and (ii) achieves near linear scaling. That theory selected which orbitals to correlate based only on the distances between the centers of different, localized orbitals, and the approximate potential energy surfaces were characterized as smooth using only visual identification. This paper now extends our previous algorithm in three important ways. First, locality is now based on both the distances between the centers of orbitals as well as the spatial extent of the orbitals. We find that, by accounting for the spatial extent of a delocalized orbital, one can account for electronic correlation in systems with some electronic delocalization using fast correlation methods designed around orbital locality. Second, we now enforce locality on not just the amplitudes (which measure the exact electron-electron correlation), but also on the two-electron integrals themselves (which m...Continue Reading

References

Apr 2, 2002·Journal of Computational Chemistry·Shuhua LiYuansheng Jiang
Jul 21, 2004·The Journal of Chemical Physics·Nicholas J Russ, T Daniel Crawford
Jan 7, 2005·The Journal of Chemical Physics·N Flocke, Rodney J Bartlett
Aug 27, 2005·The Journal of Chemical Physics·Joseph E Subotnik, Martin Head-Gordon
Feb 3, 2006·The Journal of Physical Chemistry. a·Tomica HrenarHans-Joachim Werner
Jul 20, 2006·The Journal of Chemical Physics·Alexander A Auer, Marcel Nooijen
Aug 12, 2006·Physical Chemistry Chemical Physics : PCCP·Yihan ShaoMartin Head-Gordon
Sep 1, 2006·The Journal of Chemical Physics·Joseph E SubotnikMartin Head-Gordon
Nov 23, 2006·The Journal of Chemical Physics·Ricardo A Mata, Hans-Joachim Werner
Oct 25, 2007·Physical Chemistry Chemical Physics : PCCP·Joseph E SubotnikMartin Head-Gordon

❮ Previous
Next ❯

Citations

Sep 26, 2009·The Journal of Chemical Physics·Wei LiShuhua Li
Jan 26, 2011·The Journal of Chemical Physics·Ricardo A Mata, Hermann Stoll
Jul 17, 2009·The Journal of Chemical Physics·Alexander A Auer
Dec 5, 2012·The Journal of Chemical Physics·Dipayan Datta, Marcel Nooijen
Apr 17, 2009·The Journal of Chemical Physics·Joseph E SubotnikAbraham Nitzan
Jan 25, 2013·The Journal of Chemical Physics·Christoph Riplinger, Frank Neese
Apr 17, 2012·The Journal of Chemical Physics·Jun YangHans-Joachim Werner
Apr 17, 2009·The Journal of Chemical Physics·Andrew G Taube, Rodney J Bartlett
Mar 5, 2009·The Journal of Chemical Physics·John A ParkhillMartin Head-Gordon
Nov 18, 2015·Journal of Chemical Theory and Computation·Sara I L Kokkila SchumacherTodd J Martínez
Mar 17, 2017·The Journal of Chemical Physics·Paul M Zimmerman
May 7, 2010·Physical Chemistry Chemical Physics : PCCP·Ricardo A Mata
Jan 28, 2012·Chemical Society Reviews·Mark P WallerStefan Grimme
Jan 22, 2018·The Journal of Chemical Physics·J Segarra-MartíF Aquilante
Nov 24, 2019·The Journal of Chemical Physics·Srimukh Prasad VecchamMartin Head-Gordon
Sep 11, 2009·The Journal of Physical Chemistry. a·Jonathan M MullinMark S Gordon
Feb 10, 2009·Journal of Chemical Theory and Computation·Joachim Friedrich, Michael Dolg
Jan 7, 2010·The Journal of Physical Chemistry. a·Zahra TabookhtCoen de Graaf
Jun 8, 2021·Journal of Chemical Theory and Computation·John Mark P Martirez, Emily A Carter
Aug 27, 2011·Chemical Reviews·Mark S GordonLyudmila V Slipchenko
Feb 14, 2012·Journal of Chemical Theory and Computation·Hai-Anh LeRyan P A Bettens
Nov 8, 2011·Journal of Chemical Theory and Computation·Shuhao Wen, Gregory J O Beran
Nov 19, 2015·Journal of Chemical Theory and Computation·Jun Zhang, Michael Dolg
Oct 28, 2021·Journal of Chemical Theory and Computation·Qiujiang Liang, Jun Yang

❮ Previous
Next ❯

Software Mentioned

LCCSD
CHEM
MP2
RI

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.