Vibrational Spectroscopy and State-Specific Dissociation Dynamics for Vinyl Chloride Cation in the State.

C2H335Clin the ground vibronic state was generated by one-photon mass-analyzed threshold ionization spectrometry, and its photodissociation in the 461−406 nm range was investigated. Ionization energy to the ground state of C2H335Clwas 10.0062 ± 0.0006 eV while its state onset was higher by 2.7456 ± 0.0003 eV. A vibrational spectrum of the cation in the state obtained by recording the product ion yield as a function of wavelength was analyzed by referring to the quantum chemical results at the TDDFT/B3LYP/6-311(df,pd) level. Analysis of product time-of-flight profiles recorded with different laser polarization angles showed that the dissociation pathway for the cation in the state changed with the vibrational energy, from internal conversion to and statistical dissociation therein to curve crossing to and repulsive dissociation therein. → curve crossing seemed to occur along a direction close to the C−Cl bond stretch. [ABSTRACT FROM AUTHOR]