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dc.contributor.authorChang, Shu-Weien_US
dc.contributor.authorWitek, Henryk A.en_US
dc.date.accessioned2014-12-08T15:28:33Z-
dc.date.available2014-12-08T15:28:33Z-
dc.date.issued2012-11-01en_US
dc.identifier.issn1549-9618en_US
dc.identifier.urihttp://dx.doi.org/10.1021/ct2006924en_US
dc.identifier.urihttp://hdl.handle.net/11536/20647-
dc.description.abstractAn extensive critical evaluation of intruder state removal techniques (aka shift techniques) applicable to multireference perturbation theory (MRPT) shows that the magnitude of the shift parameter a does not influence the spectroscopic parameters of diatomics to a significant degree, provided that the shift is chosen to be sufficiently large. In such case, typical variation of spectroscopic parameters over a wide range of shift parameters is smaller than 0.005 angstrom for equilibrium distances, 30 cm(-1) for harmonic vibrational frequencies, and 0.1 eV for dissociation energies. It is found that large values of a not only remove intruder states but they also bring the MRPT energies and properties closer to experimental values. The presented analysis allows us to determine optimal values of the shift parameters to be used in conjunction with various versions of MRPT; these values are recommended to replace the ad hoc values of sigma suggested in MRPT manuals in calculations for diatomics. Transferability of the optimal shift parameters to larger molecular systems and to other basis sets than aug-cc-pVTZ is anticipated but remains to be formally established.en_US
dc.language.isoen_USen_US
dc.titleChoice of Optimal Shift Parameter for the Intruder State Removal Techniques in Multireference Perturbation Theoryen_US
dc.typeArticleen_US
dc.identifier.doi10.1021/ct2006924en_US
dc.identifier.journalJOURNAL OF CHEMICAL THEORY AND COMPUTATIONen_US
dc.citation.volume8en_US
dc.citation.issue11en_US
dc.citation.spage4053en_US
dc.citation.epage4061en_US
dc.contributor.department應用化學系zh_TW
dc.contributor.department應用化學系分子科學碩博班zh_TW
dc.contributor.departmentDepartment of Applied Chemistryen_US
dc.contributor.departmentInstitute of Molecular scienceen_US
dc.identifier.wosnumberWOS:000311191900008-
dc.citation.woscount3-
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