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Molybdenum (VI) dioxodihalides: Agreement with experiment and prediction of unknown properties through density functional theory
Author(s) -
Torrent M.,
Gili P.,
Duran M.,
Solà M.
Publication year - 1997
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1997)61:3<405::aid-qua7>3.0.co;2-#
Subject(s) - density functional theory , chemistry , molybdenum , transferability , homo/lumo , excitation , atom (system on chip) , spectral line , bond length , time dependent density functional theory , atomic physics , computational chemistry , crystallography , molecule , physics , inorganic chemistry , crystal structure , statistics , mathematics , organic chemistry , logit , quantum mechanics , astronomy , computer science , embedded system
Density functional calculations are reported for the molecular structures, harmonic vibrational frequencies, UV/visible spectra, and oxo‐transferability of MoO 2 X 2 (X = F, Cl, Br, I). Available experimental data have been used to check the validity of the theoretical calculations. Given the good agreement between theory and gas‐phase experiment, predictions have been issued for the less studied members of this family of compounds. Furthermore, electronic spectra of the full series have been computed for the first time. For all transitions studied, excitation energies decrease in the order F > Cl > Br > I. Finally, the labilization of Mo(SINGLE BOND)O bonds generated by the HOMO(SINGLE BOND)LUMO transition, which is related to the oxygen‐atom transfer reaction in the active site of molybdenum oxidoreductases, was also investigated. For MoO 2 Cl 2 and MoO 2 Br 2 compounds, the HOMO‐LUMO transition yields a considerable lengthening of the Mo(SINGLE BOND)O bond, yet not requiring a large excitation energy. © 1997 John Wiley & Sons, Inc.