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Theoretical investigation of μ‐O‐bridged dinuclear Re complexes: Electronic structure, bonding nature, and absorption spectra
Author(s) -
Nakao Yoshihide,
Saito Ken,
Sakaki Shigeyoshi
Publication year - 2009
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/qua.22172
Subject(s) - chemistry , ground state , excited state , absorption spectroscopy , crystallography , amine gas treating , spectral line , perturbation theory (quantum mechanics) , absorption (acoustics) , atomic physics , computational chemistry , physics , quantum mechanics , organic chemistry , acoustics
The ground state and some low‐lying excited states of [Re 2 IV (μ‐O) 2 (NH 3 ) 8 ] 4+ ( 1 ) and [Re III Re IV (μ‐O) 2 (NH 3 ) 8 ] 3+ ( 2 ) were theoretically investigated with the second‐order Møller–Plesset perturbation theory (MRMP2) and B3LYP methods. Their ground states were assigned to be the 7 B and 6 B states, respectively, by the B3LYP method, but to be the 1 A and 2 B states, respectively, by the MRMP2 method. In 1 , the DFT‐optimized ReRe distance of the 7 B state differs much from the experimental value of similar complex such as [Re 2 IV (μ‐O) 2 (Metpa) 2 ] ( A1 ) and [Re 2 IV (μ‐O) 2 (Me2tpa) 2 ] ( A2 ) (Metpa: ((6‐methyl‐2‐pyridyl)‐methyl)bis(2‐pyridylmethyl)amine, Me2tpa: bis((6‐methyl‐2‐pyridyl)methyl)(2‐pyridylmethyl)amine) that of 1 A state is in good agreement with the experimental one. In 2 , the DFT‐optimized ReRe distance of the 6 B state differs much from the experimental value of the similar complex, [Re 2 IV (μ‐O) 2 (Metpa) 2 ] ( B ), too, but that of the 2 B state agrees well with the experimental value. These results indicate that the ground state of 1 and 2 are the 1 A and 2 B states, respectively, as assigned by the MRMP2 method. Two large absorption bands about 2.1 and 2.6 eV for A1 and A2 are theoretically assigned to be 1 1 B and 2 1 B states by the MRMP2 method. These energies are calculated to be 2.12 and 2.15 eV by the MRMP2 method, which are in good agreement with the experimental values of the similar complexes. Significant difference in absorption spectra of B from those of A1 and A2 are also discussed, based on MRMP2 calculations. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009