Please use this identifier to cite or link to this item: http://hdl.handle.net/20.500.12779/6555
DC FieldValueLanguage
dc.contributor.authorZen, Andreaen_us
dc.contributor.authorCoccia, Emanueleen_us
dc.contributor.authorGozem, Sameren_us
dc.contributor.authorOlivucci, Massimoen_us
dc.contributor.authorGuidoni, Leonardoen_us
dc.date.accessioned2021-03-30T16:04:09Z-
dc.date.available2021-03-30T16:04:09Z-
dc.date.issued2015-
dc.identifier.issn1549-9618en_US
dc.identifier.urihttp://hdl.handle.net/20.500.12779/6555-
dc.description206669en_US
dc.description.abstractThe penta-2,4-dieniminium cation (PSB3) displays similar ground state and first excited state potential energy features as those of the retinal protonated Schiff base (RPSB) chromophore in rhodopsin. Recently, PSB3 has been used to benchmark several electronic structure methods, including highly correlated multireference wave function approaches, highlighting the necessity to accurately describe the electronic correlation in order to obtain reliable properties even along the ground state (thermal) isomerization paths. In this work, we apply two quantum Monte Carlo approaches, the variational Monte Carlo and the lattice regularized diffusion Monte Carlo, to study the energetics and electronic properties of PSB3 along representative minimum energy paths and scans related to its thermal cis-trans isomerization. Quantum Monte Carlo is used in combination with the Jastrow antisymmetrized geminal power ansatz, which guarantees an accurate and balanced description of the static electronic correlation thanks to the multiconfigurational nature of the antisymmetrized geminal power term, and of the dynamical correlation, due to the presence of the Jastrow factor explicitly depending on electron-electron distances. Along the two ground state isomerization minimum energy paths of PSB3, CASSCF calculations yield wave functions having either charge transfer or diradical character in proximity of the two transition state configurations. Here, we observe that at the quantum Monte Carlo level of theory, only the transition state with charge transfer character can be located. The conical intersection, which becomes highly sloped, is observed only if the path connecting the two original CASSCF transition states is extended beyond the diradical one, namely by increasing the bond-length-alternation (BLA). These findings are in good agreement with the results obtained by MRCISD+Q calculations, and they demonstrate the importance of having an accurate description of the static and dynamical correlation when studying isomerization and transition states of conjugated systems.en_US
dc.language.isoenen_US
dc.relationNoneen_US
dc.relation.ispartofJOURNAL OF CHEMICAL THEORY AND COMPUTATIONen_US
dc.titleQuantum Monte Carlo Treatment of the Charge Transfer and Diradical Electronic Character in a Retinal Chromophore Minimal Modelen_US
dc.typeArticleen_US
dc.identifier.doi10.1021/ct501122zen_US
dc.identifier.pmid25821414en_US
dc.identifier.scopus2-s2.0-84924416506en_US
dc.identifier.isiWOS:000350918300017en_US
dc.relation.volume11en_US
dc.relation.issue3en_US
dc.description.firstpage992-1005en_US
dc.description.lastpage1005en_US
dc.description.thirdmissionNot applicableen_US
item.cerifentitytypePublications-
item.grantfulltextnone-
item.languageiso639-1en-
item.openairecristypehttp://purl.org/coar/resource_type/c_18cf-
item.openairetypeArticle-
item.fulltextNo Fulltext-
crisitem.author.orcid0000-0002-8247-209X-
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