Spin orbit effect into isomerization barrier of small gold Clusters. Oh D2h Fluxionality of the Au62+ cluster Investigated by relativistic methods
Abstract The O h [Au 6 2+ cluster exhibits an open shell 1 s 2 1 p 2 which trend to a more stable D 2 h isomer in 31.5 kcal/mol, as observed in the experimental [Au 6 {P(C 6 H 4 Me o)pH 2 6 cluster. By taking into account the spin orbit coupling (SOC) in O h [Au 6 2+ a resulting 1 s 1/2 2 1 p 1/2 2 closed shell superatomic configuration is obtained stabilizing such structure by about 14.7 kcal/mol, decreasing the isomerization barrier. Thus, the spin orbit term favors the O h D 2 h conformation rearrangement depicting a decrease in the calculated energy difference between both conformations, an interesting consequence which is not obtained in the hypothetical lighter counterparts.