A PROJECTED HAMILTONIAN APPROACH TO ATOMS-IN-MOLECULES

Author Institution:A method of treating polyatomic systems is presented which fully exploits their atom-in-molecule nature. Within an independent-particle model a partitioning technique is applied to the projection of a full polyatomic space into many atomic subspaces. The subspaces are then each coupled to one another in a piecewise self-consistent fashion. The inherent localized picture allows for an approximate form of the interatomic interactions without resort to neglect of any differential overlap or use of any empirical parameters. The one-electron localized orbital picture also provides an interesting interpretation of photoelectron spectra and of the associated electronic states. Some illustrative applications will be presented