Abstract
The electronic structure of the triphenylgallium molecule in the ground and electronically excited states has been calculated in the framework of the CNDO/S-CI method in sp and spd bases. The electron density in the AO's and atoms, the first ionization potential the energies and matrices of the changes in the electron density of the Sn and Tn states, the matrix elements of the spin-orbit coupling operator\(< S_i |\hat H_{SO} |T_j^\alpha > \) and\(< S_O |\hat H_{SO} |T_j^\alpha > \), the intensities and directions of polarization of the Sn → So and T2 → Tn transitions, and the phosphorescence lifetimes have been calculated. The following spectroscopic parametrization has been proposed for the Ga atom in the sp and spd bases: 1/2(Is + as) = 10.075 eV, 1/2(Ip + Ap) = 4.265 eV, 1/2(Id + Ad)=0, γ pGa =5 eV, γ dGa =O, β spGa =−7 eV, δ spdGa =−10 eV, and ξs,p,d=1.433. The influence of the d AO's on the shaping of the orbital nature of the S1 and T2 states has been analyzed.
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Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 5, pp. 584–590, September–October, 1985.
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Godik, V.A., Rodionov, A.N. & Shigorin, D.N. Quantum-chemical investigation of the influence of the vacant orbitals of the heteroatom on the shaping of the electronically excited states and luminescence-spectroscopic properties of triphenylgallium. Theor Exp Chem 21, 557–562 (1985). https://doi.org/10.1007/BF00944091
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DOI: https://doi.org/10.1007/BF00944091