A quantum dynamical treatment of symmetry-induced kinetic isotope effects in the formation of He2+.

Kinetic isotope effects for He(2)(+) formation are calculated quantum dynamically using high-quality Born-Oppenheimer (BO) potentials for two electronic states of He(2)(+) and an accurate treatment of all nonadiabatic BO corrections. The two potentials are coupled only when the helium isotopes are different, and the calculations reveal that this coupling is sufficient to allow the two sets of distinguishable reactants, (4)He(+) + (3)He or (3)He(+) + (4)He, to yield He(2)(+) with comparable efficiency over a wide temperature range. Consequently, the potential coupling provides a significant formation rate enhancement for the low isotopic symmetry reactants, as compared to the symmetrical cases (e.g., (4)He(+) + (4)He or (3)He(+) + (3)He). The computed symmetry-induced kinetic isotope effects (SIKIEs) are in substantial agreement with the available experimental results and represent the first theoretical demonstration of this unusual kinetic phenomenon. Possible application of SIKIE to ozone formation and other chemical systems is discussed.

Accurate, two-state ab initio study of the ground and first-excited states of He2+, including exact treatment of all Born-Oppenheimer correction terms.

Born-Oppenheimer (BO) potentials for the ground and first-excited electronic states of He2+ are determined using high level ab initio techniques for internuclear separations R of 1.2-100 bohrs and accurately fit to analytical functions. In the present formulation, the BO potentials are nuclear mass independent, and the corresponding BO approximation is obtained by ignoring four terms of the full rovibronic Hamiltonian. These four Born-Oppenheimer correction (BOC) terms are as follows: (1) mass polarization, (2) electronic orbital angular momentum, (3) first derivative with respect to R, and (4) second derivative with respect to R. In order to enable an exact rovibronic calculation, each of the four BOC terms are computed as a function of R, for the two electronic states and for their coupling, without any approximation or use of empirical parameters. Each of the BOC terms is found to make a contribution to the total energy over at least some portion of the range of R investigated. Interestingly, the most significant coupling contribution arises from the electronic orbital angular momentum term, which is evidently computed for the first time in this work. Although several BOC curves exhibit a nontrivial dependence on R, all are accurately fit to analytical functions. The resulting functions, together with the BO potentials, are used to compute exact rovibronic energy levels for 3He 3He+,3He 4He+) and 4He 4He+. Comparison to available high quality experimental data indicates that the present BOC potentials provide the most accurate representation currently available of both the low- and high-lying levels of the ground electronic state and the bound levels of the excited state.

First principles determination of the bound levels of HeLi-.

An analytical potential energy curve is developed from high quality ab initio calculations for the He+Li- interaction. The HeLi- electrostatic complex is found to have an Re of 18.5 bohrs and a De of 0.974 cm(-1). Numerical solution of the rovibrational Schrödinger equation with this potential indicates two bound levels, (v,J)=(0,0) and (0,1), for all naturally occurring isotopologs (i.e., 4He7Li-, 4He6Li-, 3He7Li-, and 3He6Li-). For the common isotopolog, 4He7Li-, a D0 of 0.207 cm(-1) and an R0 of 26.5 bohrs is determined.