A 193 nm laser photofragmentation time-of-flight mass spectrometric study of chloroiodomethane

The photodissociation dynamics of chloroiodomethane (CH2ICI) at 193 nm has been investigated by employing the photofragment time-of-flight (TOF) mass spectrometric method. Using tunable vacuum ultraviolet undulator synchrotron radiation for photoionization sampling of nascent photofragments, we have identified four primary dissociation product channels: CH2Cl+I(P-2(1/2))/I(P-2(3/2)), CH2I+Cl(P-2(1/2))/Cl(P-2(3/2)), CHI+HCl, and CH2+ICl. The state-selective detection of ((IP3/2)-P-2) and I(P-2(1/2)) has allowed the estimation of the branching ratio for I(P-2(1/2)):I(P-2(3/2)) to be 0.73: 0.27. Theoretical calculations based on the time-dependent density-functional theory have been also made to investigate excited electronic potential-energy surfaces, plausible intermediates, and transition structures involved in these photodissociation reactions. The translation energy distributions derived from the TOF measurements suggest that at least two dissociation mechanisms are operative for these photodissociation processes. One involves the direct dissociation from the 2(1)A' state initially formed by 193 nm excitation, leading to significant kinetic-energy releases. For the I-atom and Cl-atom elimination channels, the fragment kinetic-energy releases observed via this direct dissociation mechanism are consistent with those predicted by the impulsive dissociation models. Other mechanisms are likely predissociative or statistical in nature from the lower 1(1)A' and 1(1)A states and/or the ground (X) over tilde (1)A' state populated by internal conversion from the 2(1)A' state. On the basis of the maximum kinetic-energy release for the formation of CH2Cl+I(P-2(1/2)), we have obtained a value of 53 +/- 2 kcal/mol for the 0 K bond dissociation energy of I-CH2Cl. The intermediates and transition structures for the CHI+HCl and CH2+ICl product channels have been also investigated by ab initio quantum calculations at the MP2(full)/6-311G(d) and B3LYP(full)/6-11G(d) levels of theory. The maximum kinetic-energy releases observed for the CHI+HCl and CH2+ICl channels are consistent with the interpretation that the formation of CHI and CH2 in their ground triplet states is not favored. (c) 2005 American Institute of Physics.