TY - JOUR
T1 - Electronic structure and molecular properties of the octacyanorhenate [Re(CN)8]3- and [Re(CN)8]2- complexes
AU - David, Jorge
AU - Mendizábal, Fernando
AU - Arratia-Pérez, Ramiro
N1 - Funding Information:
This work has been supported in part by Fondecyt. 1030148, Fondecyt 1020141, UNAB-DI 12-04, UNAB-DI 20-04 and the Millennium Nucleus of Applied Quantum Mechanics and Computational Chemistry, P02-004-F.
PY - 2006/4/28
Y1 - 2006/4/28
N2 - We report scalar and four component relativistic density functional calculations on octacyanorhenate [Re(CN)8]2- and [Re(CN)8]3- complexes. The relativistic calculations predict that the molecular g-tensor of the paramagnetic [Re(CN)8]2- complex is isotropic. The calculated optical electronic transitions for both complexes with a polarizable continuum model using a time dependent density functional (TDDFT)/B3LYP formalism suggest that the [Re(CN)8]3- complex may distort towards dodecahedral geometry in solution. The electronic excitations of LMCT type of [Re(CN)8]2- are displaced at very high wavelengths with significant oscillator strength values which is characteristic of Re compounds having luminescent behaviour. Thus, our calculations predict that [Re(CN)8]2- could be luminescent.
AB - We report scalar and four component relativistic density functional calculations on octacyanorhenate [Re(CN)8]2- and [Re(CN)8]3- complexes. The relativistic calculations predict that the molecular g-tensor of the paramagnetic [Re(CN)8]2- complex is isotropic. The calculated optical electronic transitions for both complexes with a polarizable continuum model using a time dependent density functional (TDDFT)/B3LYP formalism suggest that the [Re(CN)8]3- complex may distort towards dodecahedral geometry in solution. The electronic excitations of LMCT type of [Re(CN)8]2- are displaced at very high wavelengths with significant oscillator strength values which is characteristic of Re compounds having luminescent behaviour. Thus, our calculations predict that [Re(CN)8]2- could be luminescent.
UR - http://www.scopus.com/inward/record.url?scp=84962377293&partnerID=8YFLogxK
U2 - 10.1016/j.cplett.2006.02.052
DO - 10.1016/j.cplett.2006.02.052
M3 - Article
AN - SCOPUS:84962377293
SN - 0009-2614
VL - 422
SP - 89
EP - 94
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 1-3
ER -