Calculations based on the atom-superposition and electron-delocalization molecular orbital (ASED-MO) method show that at low coverage, CO2 binds on the di-sigma ((1)), Delta, mu, and pi/mu sites in the bent configuration of lying-down, and on the I-fold, 2-fold, and 3-fold s tes in the perpendicular configuration. The surface adsorbed binding site of carbon dioxide is strongest at the dicy((1)) site and weakest at pi/mu site. Chemisorbed CO2 bends because of metal mixing with 2 pi (mu) --> 6a, CO2 orbital. The dissociation reaction occurred in two steps, with an intermediate complex composed of atomic oxygen and Tc-bonded CO. The OCO(1) angle of reaction intermediate complex structure for the dissociation reaction is 100 degrees on the Ni(1 1 1) surface. The activation energy was 1.27 eV.