jz2007897_si_001.pdf (639.95 kB)

Origin of the Enhancement of the Second Hyperpolarizabilities in Open-Shell Singlet Transition-Metal Systems with Metal–Metal Multiple Bonds

Download (639.95 kB)
journal contribution
posted on 16.12.2015, 19:46 by Hitoshi Fukui, Masayoshi Nakano, Yasuteru Shigeta, Benoît Champagne
Using the spin-unrestricted coupled-cluster method, we explore the origin of the second hyperpolarizabilities (γ) of singlet dichromium(II) and dimolybdenum(II) model systems with various bond lengths as a function of the diradical characters of the dσ, dπ, and dδ orbitals. Both systems exhibit enhanced γ values in the intermediate diradical character region, but by using a partitioning scheme, the dσ electrons are shown to play the essential role in contrast with the π-electrons of conventional organic π-conjugated systems. Then, in the equilibrium bond length region, the γ values are still governed by dσ electrons in the dichromium(II) system, although by dδ/dπ electrons in the dimolybdenum(II) system.