Ab initio investigation of the electronic structure and bonding of the HC(N2)x(+) and HC(CO)x(+) cations, x = 1, 2.
Employing the coupled-cluster approach and correlation consistent basis sets of triple and quadruple cardinality, we have investigated the electronic structure and bonding of the HC(N2)x(+) and HC(CO)x(+), x = 1, 2, molecular cations. We report geometries, binding energies and potential energy profiles. The ground states of HC(N2)+, HC(CO)+ and HC(N2)2(+), HC(CO)2(+) are of 3sigma- and 1A1 symmetries, respectively. All four charged species are well bound with binding energies ranging from 81 [HC(N2)+ (X3sigma-) --> CH+(a3pi) + N2(X1sigma(g)+)] to 178 [HC(CO)2(+)(X1A1) --> CH+(X1sigma+) + 2CO(X1sigma+)] kcal/mol. It is our belief that the X1A1 states of HC(N2)2(+) and HC(CO)2(+) are isolable in the solid state if combined with appropriate counteranions.
Papakondylis
Aristotle
A
Laboratory of Physical Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, P.O. Box 64 004, 157 10 Zografou, Athens, Greece. papakondylis@chem.uoa.gr
Mavridis
Aristides
A