Constructing Potential Energy Surfaces for Polyatomic Systems Recent Progress and New Problems英文文献资料.docVIP

HindawiPublishingCorporation AdvancesinPhysicalChemistry Volume2012,ArticleID164752,19pages doi:10.1155/2012/164752 ReviewArticle ConstructingPotentialEnergySurfacesforPolyatomicSystems: RecentProgressandNewProblems J.Espinosa-Garcia,M.Monge-Palacios,andJ.C.Corchado DepartamentodeQu′?micaF′?sica,UniversidaddeExtremadura,06071Badajoz,Spain CorrespondenceshouldbeaddressedtoJ.Espinosa-Garcia,joaquin@unex.es Received11May2011;Accepted14July2011 AcademicEditor:LaimutisBytautas Copyright?2012J.Espinosa-Garciaetal.ThisisanopenaccessarticledistributedundertheCreativeCommonsAttribution License,whichpermitsunrestricteduse,distribution,andreproductioninanymedium,providedtheoriginalworkisproperly cited. Di?erent methods of constructing potential energy surfaces in polyatomic systems are reviewed, with the emphasis put on ?tting,interpolation,andanalytical(de?nedbyfunctionalforms)approaches,basedonquantumchemistryelectronicstructure calculations. The di?erent approaches are reviewed ?rst, followed by a comparison using the benchmark H + CH4 and the H+NH3gas-phasehydrogenabstractionreactions.Di?erentkineticsanddynamicspropertiesareanalyzedforthesereactions andcomparedwiththeavailableexperimentaldata,whichpermitsonetoestimatetheadvantagesanddisadvantagesofeach method.Finally,weanalyzedi?erentproblemswithincreasingdi?cultyinthepotentialenergyconstruction:spin-orbitcoupling, molecular size, and more complicated reactions with several maxima and minima, which test the soundness and general applicabilityofeachmethod.Weconcludethat,althoughthe?eldofsmallsystems,typicallyatom-diatom,ismature,therestill remainsmuchworktobedoneinthe?eldofpolyatomicsystems. 1.Introduction tion reaction. Ab initio calculations were performed based on the multireference con?guration interaction (MRCI) method including Davidson’s correction using augmented correlation-consistent-polarized valence X-tuple zeta basis sets, with X up to 5, extrapolating the energies to the completebasisset(CBS)limit,andtakingi