DSpace Repository

Relativistic state-specific multireference perturbation theory incorporating improved virtual orbitals: application to the ground state single-bond dissociation

Show simple item record

dc.contributor.author Ghosh, A
dc.contributor.author Chaudhuri, R. K
dc.contributor.author Chattopadhyay, S
dc.contributor.author Mahapatra, U. S
dc.date.accessioned 2020-11-20T13:35:36Z
dc.date.available 2020-11-20T13:35:36Z
dc.date.issued 2015-10-05
dc.identifier.citation Journal of Computational Chemistry, Vol. 36, No. 26, pp. 1954-1972 en_US
dc.identifier.issn 0192-8651
dc.identifier.uri http://prints.iiap.res.in/handle/2248/7348
dc.description Restricted Access © John Wiley & Sons http://dx.doi.org/10.1002/jcc.24037 en_US
dc.description.abstract Using four‐component (4c) relativistic spinors, we present a computationally economical relativistic ab initio method for molecular systems employing our recently proposed second‐order state‐specific multireference perturbation theory (SSMRPT) incorporating the improved virtual orbital‐complete active space configuration interaction (IVO‐CASCI) reference wavefunction. The resulting method, 4c‐IVO‐SSMRPT [calculate one state at a time] is tested in pilot calculations on the homonuclear dimers including Li2, Na2, K2, Rb2, F2, Cl2, and Br2 through the computations of the ground state potential energy curves (PECs). As SSMRPT curbs intruder effects, 4c‐IVO‐SSMRPT is numerically stable. To our knowledge, the SSMRPT in the 4c relativistic framework has not been explored in the past. Selective spectroscopic constants that are closely related to the correct shape and accuracy of the energy surfaces have been extracted from the computed PECs. For the halogen molecules, a relativistic destabilization of the bond has been found. Relativistic and electron correlation effects need to be incorporated to get reliable estimates. Our results are in good accordance with reference theoretical and experimental data which manifests the computational accuracy and efficiency of the new 4c‐IVO‐SSMRPT method. The method opens for an improved description of MR systems containing heavy elements. The inexpensiveness of IVO‐CASCI makes 4c‐IVO‐SSMRPT method promising for studies on large systems of heavy elements. en_US
dc.language.iso en en_US
dc.publisher John Wiley & Sons en_US
dc.subject Four-component relativistic spinors en_US
dc.subject SSMRPT en_US
dc.subject IVO-CASCI en_US
dc.subject Diatomic halogens en_US
dc.subject Alkali dimers en_US
dc.subject Full dissociation energy curves en_US
dc.subject Spectroscopic constants en_US
dc.title Relativistic state-specific multireference perturbation theory incorporating improved virtual orbitals: application to the ground state single-bond dissociation en_US
dc.type Article en_US


Files in this item

This item appears in the following Collection(s)

Show simple item record

Search DSpace


Browse

My Account