First principles study of the electronic structure and bonding of Mn2

Abstract

We have examined the electronic structure and bonding of the Mn(2) molecule through multireference variational calculations coupled with augmented quadruple correlation consistent basis sets. The Mn atom has a (6)S(4s(2)3d(5)) ground state with its first excited state, (6)D(4s(1)3d(6)), located 2.145 eV higher. For all six molecular states (1)Sigma(g)(+), (3)Sigma(u)(+), (5)Sigma(g)(+), (7)Sigma(u)(+), (9)Sigma(g)(+), and (11)Sigma(u)(+)(1) correlating to Mn((6)S)+Mn((6)S), and for six undecets, i.e., (11)Pi(u), (11)Sigma(g)(+), (11)Delta(g), (11)Delta(u), (11)Sigma(u)(+)(2), and (11)Pi(g) with end fragments Mn((6)S)+Mn((6)D), complete potential energy curves have been constructed for the first time. We prove that the bonding in Mn(2) dimer is of van der Waals type. The interaction of two Mn (6)S atoms is hardly influenced by the total spin, as a result the six Sigma states, singlet ((1)Sigma(g)(+)) to undecet ((11)Sigma(u)(+)(1)), are in essence degenerate packed within an energy interval of about 70 cm(-1). Their ordering follows the spin multiplicity, the ground state being a singlet, X (1)Sigma(g)(+), with binding energy D(e) (D(0)) approximately 600 (550)cm(-1) at r(e) approximately 3.60 A. The six undecet states related to the Mn((6)S)+Mn((6)D) manifold, are chemically bound with binding energies ranging from 3 ((11)Pi(g)) to 25 ((11)Pi(u))kcal/mol and bond distances about 1 A shorter than the states of the lower manifold, Mn((6)S)+Mn((6)S). The lowest of the undecets is of Pi(u) symmetry located 30 kcal/mol above the X (1)Sigma(g)(+) state.