Inelastic excitation and charge transfer processes for oxygen in collision with H atoms.

Potential energy functions of the OH molecule are investigated from small to large inter-atomic distances R. The electronic problem is treated using an efficient Full Configuration Interaction (Full CI) approach that avoids orbital jumps found usually in multi-configuration self-consistent-field followed by multi-reference configuration interaction calculations of excited states. The calculations are performed for all the doublet, quartet, and sextet OH molecular states, up to the O(2p34s 3S) + H(1s 2S) asymptote, and for the lowest O- + H+ and O+ + H- ionic states. Inter-atomic distances, ranging from 0.5 Å to 20 Å, are spanned with a very small step in order to describe accurately the avoided crossings between the adiabatic potential energy functions. The accuracy of the potentials at small and large R values is analyzed. These Full CI calculations provide for the first time a global description of the 40 lowest molecular states of OH, well suited for dynamical calculations. The resulting potentials are used to obtain first estimates of cross sections and rate coefficients for different inelastic processes through the multichannel approach. This method, based on a Landau-Zener formalism taking into account the ionic-covalent avoided crossings at large distances, gives reliable results for the most intense transitions. It is shown that the largest rate coefficients correspond to mutual neutralization and ion-pair production processes.

Calcium-hydrogen interactions for collisional excitation and charge transfer.

The accurate highly correlated ab initio calculations for ten low lying covalent Σ+2 states of CaH molecule, and one ionic Ca+H- state, are performed using large active space and extended basis set, with special attention to the long-range (6-20 Å) region where a number of avoided crossings between ionic and covalent states occur. These states are further transformed to a diabatic representation using a numerical diabatization scheme based on the minimization of derivative coupling. This results in a smooth diabatic Hamiltonian which can be easily fit to an analytic form. The diagonal elements of the diabatic potentials were then empirically corrected to reproduce experimental dissociation energies. Though the emphasis is on the asymptotic region, the obtained spectroscopic constants are in good agreement with available experimental and theoretical data. The resulting analytical Hamiltonian, after back transformation to adiabatic representation, is used to obtain cross sections for different inelastic processes using both the multichannel and the branching probability current approaches. It is shown that while for most intense transitions both approaches provide very close results, the multichannel approach underestimates the cross sections of weak transitions, as a consequence of the short-range avoided crossings that are accounted for only in the branching probability current method.

Mg2H2: new insight on the Mg-Mg bonding and spectroscopic study.

The six dimensional potential energy surface of the electronic ground state X̃(1)Σ(g)(+) of Mg(2)H(2) has been generated by the coupled-cluster approach with single, double and perturbative triple excitations [CCSD(T)] combined with the aug-cc-pCVTZ basis set for Mg atoms and the aug-cc-pVTZ basis set for the H atoms. The analytical representation of this surface was used in variational calculations of the rovibrational energies of Mg(2)H(2), Mg(2)D(2), and HMg(2)D for J = 0 and 1. For Mg(2)H(2), the rotational constant B(0) is computed to be 0.1438 cm(-1), and the fundamental anharmonic wavenumbers are calculated to be ν(1) = 1527.3 cm(-1) (Σ(g)(+)), ν(2) = 275.3 cm(-1) (Σ(g)(+)), ν(3) = 1503.6 cm(-1) (Σ(u)(+)), ν(4) = 312.9 cm(-1) (Π(g)), and ν(5) = 256.5 cm(-1) (Π(u)). In addition, the electronic ground states of Mg(2)H, MgH(2), Mg(2), and MgH have been investigated in order to compute the bonding energies of Mg(2)H(2) and to explain the strength of the Mg-Mg bond in this tetra-atomic molecule. The nature of the low-lying excited states of Mg(2)H(2) is also studied.