An ab initio study of the low-lying doublet states of linear and T-shaped Ga.N-2

Lee, E. P. F. and Dyke, J. M. (2000) An ab initio study of the low-lying doublet states of linear and T-shaped Ga.N-2. Journal of Physical Chemistry A, 104 (50), 11810-11815. (doi:10.1021/jp002869+).

Abstract

The lowest-lying (2)Pi and (2)Sigma states (linear structure), and (2)A(1), B-2(1), and B-2(2) states (T-shaped structure) of the Ga .N-2 complex were studied by ab initio calculations. The B3LYP, MP2, QCISD, and CCSD(T) methods were employed with various all-electron and ECP basis sets to obtain reliable minimum-energy geometries and harmonic vibrational frequencies for these electronic states. The ground state was found to be the (X) over tilde (2)Pi state; the other states considered were of ca. 300 cm(-1) higher in energy. The interaction energy (including the full counterpoise correction for basis set superposition error and relativistic correction) of complex formation, DeltaE(e)(CP) (Ga .N-2 (X) over tilde (2)Pi), was calculated to be -1.1 kcal.mol(-1) (-400 cm(-1)) at the RCCSD(T)level with basis sets of better than augmented-polarized-valence-quadruple-zeta quality. The best estimates of Do and enthalpy of formation at 298 K for the (X) over tilde (2)Pi (1/2,3/2) spin-orbit states are D-0 = 95, 320 cm(-1) and DeltaH(298K) = 0.07, -0.58 kcal.mole(-1), respectively. Both spin-orbit components of the (X) over tilde (2)Pi state of Ga .N-2 are weakly bound at 0 K. The complex formation of the (X) over tilde (2)Pi (3/2) and (X) over tilde (2)Pi (3/2) states are slightly endothermic and exothermic, respectively, at room temperature.

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