Electronic structure and bonding of ozone

The ground and low-lying states of ozone (O(3)) have been studied by multireference variational methods and large basis sets. We have constructed potential energy curves along the bending coordinate for (1,2) (1)A’, (1,2) (1)A ‘’, (1,2) (3)A’, and (1,2) (3)A ‘’ symmetries, optimizing at the same time the symmetric stretching coordinate. Thirteen minima have been located whose geometrical and energetic characteristics are in very good agreement with existing experimental data. Special emphasis has been given to the interpretation of the chemical bond through valence-bond-Lewis diagrams; their appropriate use captures admirably the bonding nature of the O(3) molecule. The biradical character of its ground state, adopted long ago by the scientific community, does not follow from a careful analysis of its wave function. (C) 2008 American Institute of Physics

Electronic structure and bonding of the 3d transition metal borides, MB, M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, and Cu through all electron ab initio calculations

The electronic structure and bonding of the ground and some low-lying states of all first row transition metal borides (MB), ScB, TiB, VB, CrB, MnB, FeB, CoB, NiB, and CuB have been studied by multireference configuration interaction (MRCI) methods employing a correlation consistent basis set of quintuple cardinality (5Z). It should be stressed that for all the above nine molecules, experimental results are essentially absent, whereas with the exception of ScB and CuB the remaining seven species are studied theoretically for the first time. We have constructed full potential energy curves at the MRCI/5Z level for a total of 27 low-lying states, subsequently used to extract binding energies, spectroscopic parameters, and bonding schemes. In addition, some 20 or more states for every MB species have been examined at the MRCI/4Z level of theory. The ground state symmetries and corresponding binding energies (in kcal/mol) are (5)Sigma(-)(ScB), 76; (6)Delta(TiB), 65; (7)Sigma(+)(VB), 55; (6)Sigma(+)(CrB), 31; (5)Pi(MnB), 20; (4)Sigma(-)(FeB), 54; (3)Delta(CoB), 66; (2)Sigma(+)(NiB), 79; and (1)Sigma(+)(CuB), 49. (c) 2008 American Institute of Physics