ADIABATIC 3-DIMENSIONAL SIMULATIONS OF THE IHI-, BRHI-, AND BRHBR- PHOTOELECTRON-SPECTRA

In order to better characterize the transition-state region for the I + HI, Br + HI, and Br + HBr reactions, the photoelectron spectra of IHI-, IDI-, BrHI-, BrHBr-, and BrDBr- have been simulated using a three-dimensional adiabatic approach. This method of simulation uses a Born-Oppenheimer separation in time scales between the fast hydrogen-atom motion and the slow halogen-atom motion to greatly simplify the computation of the photoelectron spectrum. The resulting simulations are compared to the experimental photoelectron and threshold photodetachment spectra of these anions, and to "exact" simulations of the IHI- and IDI- spectra. The comparison with the exact simulations shows that the adiabatic method is reasonably accurate, and is a considerable improvement over previous approximate simulation schemes. Potential-energy surfaces for the I + HI and Br + HI reactions are evaluated based on a comparison between the simulated and experimental spectra. A three-dimensional surface for the Br + HBr reaction that reproduces the experimental photoelectron spectrum is constructed by extending a fitted collinear surface to three dimensions.