Vibrational spectroscopy and state-specific dissociation dynamics for vinyl chloride cation in the B state.
C(2)H(3)(35)Cl+ in 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 C(2)H(3)(35)Cl+ was 10.0062 +/- 0.0006 eV while its B state onset was higher by 2.7456 +/- 0.0003 eV. A vibrational spectrum of the cation in the B 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 B state changed with the vibrational energy, from internal conversion to X and statistical dissociation therein to curve crossing to C and repulsive dissociation therein. B --> C curve crossing seemed to occur along a direction close to the C-Cl bond stretch.
Lee
Mina
M
Department of Chemistry, Seoul National University, Seoul 151-742, Korea.
Kim
Myung Soo
MS
D002412:Cations; D003198:Computer Simulation; D007700:Kinetics; D013058:Mass Spectrometry; D008956:Models, Chemical; D011789:Quantum Theory; D014732:Vibration; D014752:Vinyl Chloride / Q000737:chemistry*
D002412:Cations; D014752:Vinyl Chloride