Journal of Physical Chemistry, Vol.99, No.32, 12141-12150, 1995
Electronic-Transition Oscillator Strength by the Extended Huckel Molecular-Orbital Method
Calculations of the oscillator strength of electronic dipole-induced transitions (EDiTs) based on EHMO wave functions including all transition matrix elements offer a generally applicable method for computing intensities of all types of transitions found in molecules, clusters, and complexes. Application of this EHMO-EDiT procedure to formaldehyde, MnO4-, p-(N,N-dimethylamino)benzonitrile (DMABN), 2,2’-bipyridyl (bpy), Ru(bpy)(3)(2+), and [CO(CO)(4)(H7Si8O12)] illustrates the versatility of this procedure and offers new insight into some "old problems". We find that the TICT state of DMABN is expected to live long enough to relax to a state described by the (b(1))(1)(b(2))(1) configuration. Emission of a photon in this state is forbidden by symmetry. However, a small twist of the dialkylamino group by only 15 degrees increases this oscillator strength along the z axis enormously. TICT emission has empirically been shown to be z-polarized and strong in intensity. The emission rates can be thermally activated. This is in good qualitative agreement with the oscillator strength calculation. We also find that the intensities of the two z-polarized pi* <-- pi transitions depend relatively little on the amino group torsional angle. This dependence is indeed characteristic for the TICT state. EDiT calculations on bpy as a function of the torsional angle theta lead to a satisfactory interpretation of the two ominent pi* <-- pi transitions of this very often used ligand. The 2 pi* <-- 2n oscillator strength is very small for cis. However, the cis (2n)(1)(2 pi*)(1) configuration correlates with the trans (1 pi*)(1)(1 pi*)(1) which bears a large 1 pi* <-- 1 pi oscillator strength.
Keywords:INTRAMOLECULAR CHARGE-TRANSFER;EXCITED-STATES;COMPLEXES;PHOTOCHEMISTRY;LOCALIZATION;PHOTOPHYSICS;PARA-(N;N-DIMETHYLAMINO)BENZONITRILE;LUMINESCENCE;GEOMETRIES;SYSTEMS