Investigation of negative ion states in HCl and HF by configuration interaction methods

Abstract

Multi-reference configuration interaction calculations are employed for the study of Born-Oppenheimer potential energy curves in HF/HF^- and HCl/HCl^-. Large gaussian basis sets including negative ion functions as well as diffuse s, p and d AOs are employed thereby. In HCl^- a repulsive 2Σ⁺ state emerges from the calculations approximately 4·2 eV above the HCl X ¹Σ⁺ ground state; no such entity could be observed in HF^- in the energy range treated. All other CI roots which produce potential curves parallel to and above the X ¹Σ⁺ curve are found to possess quite diffuse charge distributions in the basis set variations undertaken and can therefore not be considered resonant states but rather as discrete representations of free-electron species in the HX + e^- continuum. For large internuclear distances the HF^- and HCl^- curves lie below those of the neutral species, whereby the crossing between the X ²Σ⁺ ionic and X ¹Σ⁺ curves are calculated to occur at 3·2 a ₀ in HCl/HCl^- and 2·6 a ₀ in HF/HF^-. Finally it is argued that non-adiabatic effects involving the low energy HX^- continuum states in the Born-Oppenheimer approximation and the bound HX^- species at large internuclear separations (with continuation inside the HX potential well) are ultimately responsible for observed electron scattering resonances, in accordance with recent work of Domcke and Cederbaum and of Nesbet.