Photofragmentation dynamics of ICN−(CO2)n clusters following visible excitation

Joshua P. Martin, Amanda S. Case, Quanli Gu, Joshua P. Darr, Anne B. McCoy, W. Carl Lineberger
2013 Journal of Chemical Physics  
Photodissociation of ICN − (CO 2 ) n , n = 0-18, with 500-nm excitation is investigated using a dual time-of-flight mass spectrometer. Photoabsorption to the 2 1/2 state is detected using ionic-photoproduct action spectroscopy; the maximum absorption occurs around 490 nm. Ionicphotoproduct distributions were determined for ICN − (CO 2 ) n at 500 nm. Following photodissociation of bare ICN − via 430-650 nm excitation, a small fraction of CN − is produced, suggesting that nonadiabatic effects
more » ... iabatic effects play a role in the photodissociation of this simple anion. Electronic structure calculations, carried out at the MR-SO-CISD level of theory, were used to evaluate the potential-energy surfaces for the ground and excited states of ICN − . Analysis of the electronic structure supports the presence of nonadiabatic effects in the photodissociation dynamics. For n ≥ 2, the major ionic photoproduct has a mass corresponding to either partially solvated CN − or partially solvated [NCCO 2 ] − .
doi:10.1063/1.4817664 pmid:23947863 fatcat:ray6dsw5xrbkpa4xgt7wjyruja