Linear C(n) clusters: are they acetylenic or cumulenic?
Uncapped linear Cn clusters have been studied with hybrid density functional theory focusing on the geometry, HOMO-LUMO gap, and the longitudinal optical (LO) vibrational mode. The latter two correlate well with the bond length alternation (BLA) of the optimized geometry. Due to end effects, the BLA is not constant along the chains. The degree of BLA changes continuously with increasing n: starting with essentially nonalternating structures (cumulenic), then turning into strongly alternating (acetylenic) structures. This transition has not yet been described or characterized and occurs at relatively large values of n. The implications for the widely observed characteristic LO vibrational bands of linear carbon clusters are discussed.
Yang
Shujiang
S
Department of Chemistry, Georgetown University, Washington DC 20057-1227, USA.
Kertesz
Miklos
M