Electronic states and potential energy surfaces of H_{2}Te, H_{2}Po, and their positive ions
Abstract
Geometries, bond energies, ionization potentials, dipole moments, other oneelectron properties, and potential energy surfaces of six valence electronic states of H_{2}Te and H_{2}Po species are obtained using the relativistic complete active space multiconfiguration selfconsistent field (CASSCF) followed by full secondorder configuration interaction (SOCI) and relativistic configuration interaction (RCI) calculations including spinorbit coupling. In addition, Rydberg states of H_{2}Te and H_{2}Se are studied to interpret the experimental spectra.
The potential energy surfaces of two electronic states of H_{2}Te^{+} and H_{2}Po^{+} are obtained. The ground states of both H_{2}Te and H_{2}Po are found to be of X ^{1}A_{1}(A_{1}) symmetry with bent (C_{2v}) equilibrium geometries of H_{2}Te:r_{e} =1.668 Å, θ_{e}=91.2°; and H_{2}Po:r_{e} =1.835 Å and θ_{e}=90.9°. The ground states of H_{2}Te^{+} and H_{2}Po^{+} are X ^{2}B_{1} with H_{2}Te^{+}:r_{e} =1.676 Å, θ_{e}=90.7° and H_{2}Po^{+}:r_{e} =1.828 Å and θ_{e}=88°. The D_{e} (HTeH) and D_{e} (HPoH) including spinorbit effects are calculated as 63.2 and 39.4 kcal/mol, respectively. The X ^{2}B_{1}(E)A ^{2}A_{1}(E) energy separations of H_{2}Te^{+} and H_{2}Po^{+} ions are calculated as 66.6 and 76 kcal/mol, respectively. The adiabatic IPs of H_{2}Te and H_{2}Po are calculated as 8.47 and 7.79 eV, respectively. In addition CASSCF/SOCI/RCI calculations are also carried out on the X ^{2}Π_{3/2} and ^{2}Π_{1/2} states of TeH and PoH diatomics. The X ^{2}Π_{3/2}^{2}Π_{1/2} energy separations of TeH and PoH are computed as 3710 and 9920 cm^{1}, respectively. Spinorbit effects are thus found to be very significant for PoH and H_{2}Po. All excited states of H_{2}Te and H_{2}Po are above 3.7 and 3.1 eV, respectively. Properties and energy separations of H_{2}Te and H_{2}Po are compared with the lighter group (VI) H_{2}Ch species.
 Publication:

Journal of Chemical Physics
 Pub Date:
 June 1990
 DOI:
 10.1063/1.458298
 Bibcode:
 1990JChPh..92.6604S