An unbiased confirmation of the participating isomers of C2B5− in the formation of its photo-detachment spectra: a theoretical study

Abstract

The primary goal of the present article is to provide an unbiased structural confirmation of C₂B₅⁻, relying on its available experimental photo-detachment spectra. The study is performed from scratch by optimizing the lowest energy isomers of C₂B₅⁻ and later, suitable molecular vibronic Hamiltonians are constructed by analyzing the normal modes of these optimized isomers. The Hamiltonians’ parameters are evaluated from the fits of the calculated ab initio single point energies using a state of the art multireference configuration (MRCI) level of theory employing a correlation consistent polarized triple zeta (cc-pVTZ) basis set. The state-averaged variant of the MRCI level of theory is also applied to deal with the highly interactive electronic states of both of the isomers. A detailed analysis of the potential energy curves along the totally symmetric vibrational modes is performed to understand the energy modulation between the different electronic states and also to find the energetic locations of the conical intersections. The introduction of the non-symmetric vibrational modes in the Hamiltonians help to understand the impact of non-adiabaticity during energy modulation in the coupled surfaces. Later, both adiabatic and non-adiabatic nuclear dynamics are performed on the electronic states of both of the isomers using the constructed reduced and full-dimensional Hamiltonians. The results of the adiabatic dynamics are used to assign the positions of the simulated photo-detachment bands, while the non-adiabatic dynamics improve the shape of those bands. Finally, we compare our theoretical findings with the available experimental photo-detachment spectra of C₂B₅⁻ to provide an unbiased structural confirmation of the participating isomers of C₂B₅⁻ in its photo-detachment spectra.