Theoretical study of multiphoton ionization of cyclohexadienes and unimolecular decomposition of their mono- and dications

Abstract

Quantum chemical calculations of the geometric structure, vertical excitation energies, and ionization potentials for the isomeric pair of 1,3- and 1,4-cyclohexadienes and their mono- and dications have been performed employing a variety of theoretical methods and basis sets. The computed ionization potentials and electronic excitation energies are used to evaluate the range of internal energies available for fragmentation of the cations following multiphoton resonance ionization of the cyclohexadienes in intense laser field. The conditions governing the competition between multiple ionization and decomposition of the ions are also discussed. Calculations of stationary points on the potential energy surfaces for various fragmentation channels and relative product yields at different available internal energies are then utilized to analyze the trends in branching ratios of major dissociation products of the 1,4-cyclohexadiene²⁺ dication, which include C₃H₃⁺ + C₃H₅⁺, C₂H₃⁺ + C₄H₅⁺, and C₄H₃⁺ + C₂H₅⁺.