Electron localization-delocalization transitions in dissociation of the C4- anion: a large-D analysis.
We present a study, employing high level ab initio methods, of electron localization-delocalization transitions along the dissociation path of the C4- anion to C2 and C2-. We find that at the equilibrium geometry, the symmetrical and nonsymmetrical configurations of the linear C4- anion are almost isoenergetic. However, along a collinear dissociation path, the dipole moment drops abruptly to zero when the separation between the two middle carbon nuclei reaches about R = 2.15 angstroms. The dipole moment remains zero until about R = 2.78 angstroms, and then continuously increases as dissociation proceeds. This behavior is analogous to critical phenomena: The abrupt drop to zero of the dipole moment resembles a first-order phase transition, the later steady rise resembles a continuous phase transition. We show that a simple sub-Hamiltonian model, corresponding to the large-dimension limit for an electron in the field of four collinear carbon atoms, exhibits both kinds of phase transitions along the dissociation path.
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.
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