Unphysical Discontinuities in GW Methods

Journal of Chemical Theory and Computation
Mickaël VérilPierre-François Loos

Abstract

We report unphysical irregularities and discontinuities in some key experimentally measurable quantities computed within the GW approximation of many-body perturbation theory applied to molecular systems. In particular, we show that the solution obtained with partially self-consistent GW schemes depends on the algorithm one uses to self-consistently solve the quasiparticle (QP) equation. The main observation of the present study is that each branch of the self-energy is associated with a distinct QP solution and that each switch between solutions implies a significant discontinuity in the quasiparticle energy as a function of the internuclear distance. Moreover, we clearly observe "ripple" effects, i.e., when a discontinuity in one of the QP energies induces (smaller) discontinuities in the other QP energies. Going from one branch to another implies a transfer of weight between two solutions of the QP equation. The cases of occupied, virtual, and frontier orbitals are separately discussed on distinct diatomics. In particular, we show that multisolution behavior in frontier orbitals is more likely if the HOMO-LUMO gap is small.

References

Oct 15, 1986·Physical Review. B, Condensed Matter·M S Hybertsen, S G Louie
Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
Jul 23, 2004·The Journal of Chemical Physics·Neepa T MaitraKieron Burke
Sep 28, 2004·Physical Review Letters·Sergey V FaleevTakao Kotani
Nov 10, 2005·Chemical Reviews·Andreas Dreuw, Martin Head-Gordon
Jun 29, 2006·Physical Review Letters·M van SchilfgaardeS Faleev
Feb 5, 2009·The Journal of Chemical Physics·P RomanielloG Onida
Mar 26, 2009·The Journal of Chemical Physics·Adrian StanRobert van Leeuwen
Oct 2, 2009·Physical Review Letters·Pierre-François Loos, Peter M W Gill
Jun 24, 2010·The Journal of Chemical Physics·P RomanielloL Reining
Dec 14, 2011·The Journal of Chemical Physics·Pierre-François Loos, Peter M W Gill
Jun 14, 2013·Physical Review Letters·T SchäferA Toschi
Nov 25, 2014·The Journal of Chemical Physics·Alexander A RusakovDominika Zgid
Feb 16, 2015·The Journal of Chemical Physics·Qi OuJoseph E Subotnik
May 24, 2015·The Journal of Chemical Physics·Jordan J PhillipsDominika Zgid
Jul 17, 2015·The Journal of Chemical Physics·S Di SabatinoP Romaniello
Jul 25, 2015·Journal of Chemical Theory and Computation·Denis JacqueminXavier Blase
Nov 18, 2015·Journal of Chemical Theory and Computation·So HirataJ V Ortiz
Mar 11, 2014·Journal of Chemical Theory and Computation·Paul BoulangerXavier Blase
Jan 8, 2013·Journal of Chemical Theory and Computation·M J van SettenF Evers
Jan 8, 2013·Journal of Chemical Theory and Computation·Fabien Bruneval, Miguel A L Marques
Dec 9, 2015·Journal of Chemical Theory and Computation·Michiel J van SettenPatrick Rinke
Jan 6, 2016·Journal of Chemical Theory and Computation·Olga DolgounitchevaJ Vincent Ortiz
Jan 6, 2016·Journal of Chemical Theory and Computation·Joseph W KnightNoa Marom
Feb 8, 2016·The Journal of Chemical Physics·Alexander A Rusakov, Dominika Zgid
May 12, 2016·Journal of Chemical Theory and Computation·F KaplanM J van Setten
Sep 16, 2016·Journal of Chemical Theory and Computation·Fabio CarusoPatrick Rinke
Oct 27, 2016·The Journal of Chemical Physics·Shane M ParkerFilipp Furche
Dec 8, 2016·Journal of Computational Chemistry·Katharina Krause, Wim Klopper
Dec 25, 2016·The Journal of Chemical Physics·Fabien Bruneval
Jan 18, 2017·Journal of Chemical Theory and Computation·Emanuele MaggioGeorg Kresse
Jan 21, 2017·Journal of Chemical Theory and Computation·Denis JacqueminXavier Blase
Mar 31, 2017·Scientific Reports·Y Pavlyukh
Apr 8, 2017·Journal of Chemical Theory and Computation·Linda HungSerdar Öğüt

❮ Previous
Next ❯

Citations

Oct 9, 2019·The Journal of Chemical Physics·Young-Moo Byun, Serdar Öğüt
Feb 3, 2019·The Journal of Chemical Physics·Hugh G A BurtonPierre-François Loos
Sep 24, 2020·The Journal of Chemical Physics·Levi KellerDorothea Golze
Jul 30, 2019·Frontiers in Chemistry·Dorothea GolzePatrick Rinke
Sep 24, 2020·The Journal of Chemical Physics·Pierre-François Loos, Xavier Blase
Nov 15, 2020·The Journal of Chemical Physics·Juliette Authier, Pierre-François Loos
Mar 9, 2021·Journal of Chemical Theory and Computation·Johannes TölleJohannes Neugebauer
Mar 17, 2021·Journal of Chemical Theory and Computation·Enzo Monino, Pierre-François Loos
Apr 3, 2021·Journal of Chemical Theory and Computation·Ivan Duchemin, Xavier Blase
Aug 4, 2021·The Journal of Chemical Physics·Jason M YuFilipp Furche
Aug 6, 2021·The Journal of Physical Chemistry Letters·Oliver J BackhouseGeorge H Booth
Dec 12, 2020·Journal of Chemical Theory and Computation·J Arjan BergerPina Romaniello
Jan 1, 2020·Journal of Chemical Theory and Computation·Pierre-François LoosJulien Toulouse
Feb 12, 2020·The Journal of Physical Chemistry Letters·Dorothea GolzePatrick Rinke
Apr 17, 2020·The Journal of Physical Chemistry Letters·Pierre-François LoosXavier Blase
Jun 14, 2019·Journal of Chemical Theory and Computation·Fabien Bruneval
May 15, 2019·Journal of Chemical Theory and Computation·Yann GarnironAnthony Scemama
Aug 14, 2020·The Journal of Physical Chemistry Letters·Xavier BlasePierre-François Loos
Feb 6, 2020·Journal of Chemical Theory and Computation·Ivan Duchemin, Xavier Blase
Aug 8, 2019·Journal of Chemical Theory and Computation·S Di SabatinoP Romaniello
Nov 16, 2021·Frontiers in Chemistry·S Di SabatinoP Romaniello

❮ Previous
Next ❯

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.