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Photodissociation of carbon dioxide in singlet valence electronic states. I. Six multiply intersecting

*ab initio* potential energy surfaces

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10.1063/1.4808369

### Abstract

The global potential energy surfaces of the first six singlet electronic states of CO2, 1—31 A′, and 1—31 A″ are constructed using high level ab initio calculations. In linear molecule, they correspond to , 11Δ u , , and 11Π 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 × 5 potential matrix is constructed, which can be used in quantum mechanical calculations of the absorption spectrum of the five excited singlet valence states.

© 2013 AIP Publishing LLC

Received 08 April 2013
Accepted 20 May 2013
Published online 12 June 2013

Acknowledgments: Financial support by the Deutsche Forschungsgemeinschaft (DFG) is gratefully acknowledged.

Article outline:

I. INTRODUCTION

II. ELECTRONIC STRUCTURE CALCULATIONS

III. PROPERTIES OF THE VALENCE PESs AND THEIR CROSSINGS

A. Ground electronic state

B. Overview of the excited electronic states

C. Topography of state intersections in the FC zone

D. Intersections and avoided crossings in bent CO_{2}

E. Beyond the first six states: Valence/Rydberg crossings

IV. QUASI-DIABATIZATION OF THE VALENCE STATES

A. Intersections at bent geometries: Local diabatization

B. Intersections at linear geometries: Regularized diabatic states

V. CONCLUSIONS

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2013-06-12

2014-04-18

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