The dynamics of ICN- and ICN are investigated through a combination of experimental and theoretical studies.  In the first of these, we probe the excited state dynamics of ICN- following excitation to the lowest energy state that correlates to I- + CN products.  The observed absorption cross sections and branching ratios are obtained as a function of the excitation energy.  In the absence of solvating atoms or molecules, the excess charge localizes on the iodine.  The introduction of a single CO2 or argon atom changes the branching ratio between the three possible product channels (I- , CN- or ICN-).  Interestingly when one argon atom is introduced roughly 5% of the products undergo cage recombination to form ICN-, providing an example of single atom caging.  When CO2 is introduced, cage recombination is only seen in larger complexes, but a significant fraction of the photoproducts obtained following excitation of ICN-CO2 have the charge localized on the CN.  In a second set of studies, the photoelectron spectrum of ICN- is recorded.  The position of the peaks is consistent with earlier electronic structure studies of Morokuma and co-workers.  Low kinetic energy peaks are also observed in the photoelectron spectrum, the position and relative intensities of which change very little over a 1.5 eV range of excitation energies.  These experimental observations are analyzed using potential curves for ICN-, evaluated at the MR-SO-CISD level of theory with augmented triple-zeta basis sets for all three atoms, combined with vibrational calculations of the populated levels on the ground electronic state of the anion and wave packet studies of the dynamics following photoexcitation or photodetachment of ICN-.  In interpreting the effects of Ar and CO2 on the excited state dynamics of ICN-, we draw on the results of recent studies on IBr-.

Excited state dynamics, photoelectron spectra, and potential surfaces for ICN<sup>-</sup> its complexes with argon and CO<sub>2</sub>

243rd National Meeting (2012)

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Excited state dynamics, photoelectron spectra, and potential surfaces for ICN- its complexes with argon and CO2

Excited state dynamics, photoelectron spectra, and potential surfaces for ICN^- its complexes with argon and CO₂