Coupling between dipole-bound and valence states: the nitromethane anion

Abstract

Nitromethane is a prototypical example for a molecule that can bind an extra electron in two fundamentally different ways forming dipole-bound as well as valence anions. The classification of the electronic states as dipole-bound or valence does in fact suggest a diabatic viewpoint, and we investigate the coupling between these two electronic states of the nitromethane anion. The coupling element W is extracted from a cut through the two lowest adiabatic potential energy surfaces by fitting of a simple avoided crossing model potential, that is, W is effectively approximated as half the smallest splitting. High level ab initio calculations are performed to compute the two states along the cut. We discuss in particular how a balance between the two very different electronic states can be achieved, and how the temporary nature of the valence anion in a large region of the relevant nuclear coordinate space can be taken into account. The autodetachment lifetime following vertical electron attachment to the neutral is computed, but the calculation of the temporary anion state turns out to be too expensive for a study of the two adiabatic surfaces, and consequently, the second adiabatic state is only included at geometries where it lies below the neutral potential energy surfaces. We find a coupling matrix element of 30 meV. On the one hand, this value is much smaller than the vertical excitation energies underlining the need for a diabatic picture. On the other hand, this value suggests rapid transitions on a mass spectrometric timescale substantiating the notion that the dipole bound state provides an efficient doorway for attachment to the valence state.