Photodissociation of carbon dioxide in singlet valence electronic states. I. Six multiply intersecting ab initio potential energy surfaces

TL;DR

This paper constructs detailed potential energy surfaces for the first six singlet electronic states of CO2, revealing complex intersections and diabatization useful for modeling UV absorption spectra.

Contribution

It provides high-level ab initio potential energy surfaces for six CO2 singlet states, including their intersections and a diabatic matrix for spectral calculations.

Findings

Accurate benchmarks for all six states.

Identification of multiple intersections and conical crossings.

Construction of a diabatic 5x5 potential matrix.

Abstract

The global potential energy surfaces of the first six singlet electronic states of CO$_2$, 1---3$^1/!A'$ and 1---3$^1/!A"$ are constructed using high level ab initio calculations. In linear molecule, they correspond to $\tilde{X}^1\Sigma_g^+$, $1^1\Delta_u$, $1^1\Sigma_u^-$, and $1^1\Pi_g$. The calculations accurately reproduce the known benchmarks for all states and establish missing benchmarks for future calculations. The calculated states strongly interact at avoided crossings and true intersections, both conical and glancing. Near degeneracies can be found for each pair of six states and many intersections involve more than two states. In particular, a fivefold intersection dominates the Franck-Condon zone for the ultraviolet excitation from the ground electronic state. The seam of this intersection traces out a closed loop. All states are diabatized, and a diabatic $5\times 5$ potential matrix is constructed, which can be used in quantum mechanical calculations of the absorption spectrum of the five excited singlet valence states.