Abstract
Ab initio based multireference singles and doubles configuration interaction (MRDCI) calculations are performed on the ground and low-lying electronic states of GaP using semi-core relativistic effective core potentials and spin-orbit operators. Potential energy curves of 39 Λ-S states which correlate with three lowest dissociation limits of GaP have been computed. Spectroscopic constants of 17 bound states upto the energy of 47 400cm−1 are estimated. The ground state (X3Σ−) electronic configuration of GaP is found to be σ12σ22σ32π2 with re=2.5Å and ωe=268cm−1. The best possible dissociation energy (De) of the ground state is calculated to be 39kcals/mol which is smaller than the available experimental value by 15kcals/mol. Effects of the spin-orbit coupling on the potential energy curves and spectroscopic constants of those electronic states which correlate with lowest two dissociation limits have been investigated. Spectroscopic properties of the spin-orbit states arising from lowest ten Λ-S states have been calculated. Electric dipole-allowed transitions like 3Π–X3Σ−, 33Π–3Π, 23Σ+–3Π, and 21Π–1Π are found to be more probable. Lifetimes of seven excited states: 41Σ+, 21Σ+, 21Π, 23Σ+, 3Σ+, 23Π, and 33Π are estimated. The 33Π and 23Σ+states are found to be short-lived with the radiative lifetimes lying between 0.01 and 0.2μs.
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