An ab initio study of Xe–NO(X2II) and Xe–NO(A2Σ+) potential energy surfaces

Abstract

The potential energy surfaces (PESs) of Xe-NO(X 2 ) and Xe-NO(A 2 + ) complexes have been obtained using highly accurate ab initio calculations. Analytical representations of these PESs were obtained using a Legendre polynomial interpolation. In the ground state, the surfaces A and A show two linear wells at short distances (4.0-4.5 Å) with energies between -67 and -135 cm -1 . The surface A , unlike that of A , presents a T-shape well at -85 cm -1 . To evaluate the influence of corrections for quadruple excitations on the topology of the Xe-NO(A 2 + ) PES, calculations were performed with and without considering corrections for quadruple excitations. Both surfaces present two linear wells between 4.9 and 6.8 Å but when considering corrections for quadruple excitations the wells are more than twice as deep (-64 and -40 cm -1 ) as when not considering these corrections (-25 and -20 cm -1 ).