Multireference configuration interaction study of the predissociation of C2 via its F1Πu state

Abstract

Photodissociation is one of the main destruction pathways for dicarbon (C2) in astronomical environments, such as diffuse interstellar clouds, yet the accuracy of modern astrochemical models is limited by a lack of accurate photodissociation cross sections in the vacuum ultraviolet range. C2 features a strong predissociative [Formula: see text] electronic transition near 130 nm originally measured in 1969; however, no experimental studies of this transition have been carried out since, and theoretical studies of the F1Π u state are limited. In this work, potential energy curves of excited electronic states of C2 are calculated with the aim of describing the predissociative nature of the F1Π u state and providing new ab initio photodissociation cross sections for astrochemical applications. Accurate electronic calculations of 56 singlet, triplet, and quintet states are carried out at the DW-SA-CASSCF/MRCI+Q level of theory with a CAS(8,12) active space and the aug-cc-pV5Z basis set augmented with additional diffuse functions. Photodissociation cross sections arising from the vibronic ground state to the F1Π u state are calculated by a coupled-channel model. The total integrated cross section through the F1Π u v = 0 and v = 1 bands is 1.198 × 10−13 cm2 cm−1, giving rise to a photodissociation rate of 5.02 × 10−10 s−1 under the standard interstellar radiation field, much larger than the rate in the Leiden photodissociation database. In addition, we report a new [Formula: see text] state that should be detectable via a strong [Formula: see text] band around 116 nm.