Intensity of d-d symmetry-forbidden electronic transition in Cr(CO)6.
Absolute absorption intensities (oscillator strengths) are calculated for the d-d symmetry-forbidden transition in hexacarbonyl chromium. The vibronic coupling mechanism is taken into account in a way that represents an alternative to the traditional perturbative approach of Herzberg and Teller. In the so-called direct method, the electronic transition moment is directly expanded in a power series of the vibrational normal coordinates of suitable symmetry. In the present case, i.e., d-d ligand field transitions, or more specifically (1)A(1g) --> (1)T(1g) and (1)A(1g) --> (1)T(2g) transitions, the dipole selection rule is broken by vibronic interaction induced by normal modes that transform like T(1u) and T(2u) representations of the O(h) group. An analysis of the relative importance of normal modes in promoting electronic transitions is carried out.
Rocha
Alexandre B
AB
Instituto de Química, Departamento de Físico-Qímica, Universidade Federal do Rio de Janeiro, Cidade UniversitAria, CT Bloco A. Rio de Janeiro, 21941-909 Rio de Janeiro, Brazil. rocha@iq.ufrj.br