Axial ligand effects on the diradical characters and second hyperpolarizabilities of open-shell singlet transition-metal dinuclear complexes

作者：Yamada Taishi; Takamuku Shota; Matsui Hiroshi; Champagne Benoit; Nakano Masayoshi^*

来源：Chemical Physics Letters, 2014, 608: 68-73.

DOI：10.1016/j.cplett.2014.05.064

We investigate the axial ligand effects on the diradical character (y) dependences of the second hyperpolarizabilities (gamma) of transition-metal dinuclear complexes, Mo(I)(2)(CO)(2), with different bond lengths (R) using the spin-unrestricted coupled-cluster method. Mo(I)(2)(CO)(2) exhibits intrinsic y-gamma correlation and dominant d sigma-electron contribution to the maximum gamma (gamma(max)), which are also observed in the bare dinuclear analogs. The axial-ligand coordination to Mo(I)(2) is found to cause the increase of the diradical character of the d sigma orbital, the emergence of large negative gamma for small R, and an enhancement of |gamma(max)| by a factor of similar to 30 as compared to the bare analogs.

• 出版日期2014-7-21