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Excited states of OsO 4 : A comprehensive time‐dependent relativistic density functional theory study
Author(s) -
Zhang Yong,
Xu Wenhua,
Sun Qiming,
Zou Wenli,
Liu Wenjian
Publication year - 2010
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21344
Subject(s) - excited state , coupled cluster , relativistic quantum chemistry , atomic physics , physics , hamiltonian (control theory) , valence (chemistry) , atomic orbital , excitation , density functional theory , ionization , scalar (mathematics) , quantum mechanics , chemistry , ion , molecule , electron , mathematical optimization , mathematics , geometry
A large number of scalar as well as spinor excited states of OsO 4 , in the experimentally accessible energy range of 3–11 eV, have been captured by time‐dependent relativistic density functional linear response theory based on an exact two‐component Hamiltonian resulting from the symmetrized elimination of the small component. The results are grossly in good agreement with those by the singles and doubles coupled‐cluster linear response theory in conjunction with relativistic effective core potentials. The simulated‐excitation spectrum is also in line with the available experiment. Furthermore, combined with detailed analysis of the excited states, the nature of the observed optical transitions is clearly elucidated. It is found that a few scalar states of 3 T 1 and 3 T 2 symmetries are split significantly by the spin‐orbit coupling. The possible source for the substantial spin‐orbit splittings of ligand molecular orbitals is carefully examined, leading to a new interpretation on the primary valence photoelectron ionization spectrum of OsO 4 . © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010