Dissociative electron attachment to the H2O molecule. I. Complex-valued potential-energy surfaces for the 2B1, 2A1, and 2B2 metastable states of the water anion

TL;DR

This paper develops detailed complex-valued potential-energy surfaces for metastable states of the water anion, crucial for understanding dissociative electron attachment to water, combining advanced quantum calculations.

Contribution

It provides the first comprehensive three-dimensional complex potential-energy surfaces for water anion metastable states, including diabatization across a conical intersection.

Findings

Constructed global potential-energy surfaces for water anion states.

Analyzed the impact of surface shapes on nuclear dynamics.

Combined configuration-interaction and complex Kohn scattering methods.

Abstract

We present the results of calculations defining global, three-dimensional representations of the complex-valued potential-energy surfaces of the doublet B1, doublet A1, and doublet B2 metastable states of the water anion that underlie the physical process of dissociative electron attachment to water. The real part of the resonance energies is obtained from configuration-interaction calculations performed in a restricted Hilbert space, while the imaginary part of the energies (the widths) is derived from complex Kohn scattering calculations. A diabatization is performed on the 2A1 and 2B2 surfaces, due to the presence of a conical intersection between them. We discuss the implications that the shapes of the constructed potential-energy surfaces will have upon the nuclear dynamics of dissociative electron attachment to H2O. This work originally appeared as Phys Rev A 75, 012710 (2007). Typesetting errors in the published version have been corrected here.