Modeling the Photophysics of Zn and Cd Monomers, Metallophilic Dimers, and Covalent Excimers

Abstract

Density functional (Xα, BLYP, BPW91, B3LYP, and B3PW91), MP2, and coupled cluster with singles, doubles, and quasiperturbative triple excitations (CCSD(T)) methods in combination with LANL2DZ, cc-pVxZ, cc-pVxZ-PP, or cc-pVxZ-DK (where x = D (double), T (triple) Q (quadruple), and 5 (quintuple)) basis sets have been employed in computations of excited states of zinc and cadmium dimers and monomers. The spectroscopic constants r(e), D(e), T(e), ω(e), ω(e)x(e), and B(e) are compared among group 12 dimers in their ground and low-lying phosphorescent excited states. The weak metallophilic bonding in the ground state requires MP2 or CCSD(T) description, whereas the excimeric bonding is well described by CCSD(T), BLYP, B3LYP, BPW91, and B3PW91. Consistent with our previous work on Hg(n) species, absorption and phosphorescence transition energies that agree well with experimental results can be obtained with CCSD(T) and B3PW91 methods in combination with the correlation consistent basis sets of triple-ζ or higher level. This is the case for monomers and *Cd(2) and *Zn(2) lowest triplet excimers (in either the (3)Σ(u)(+) or (3)Π(g) state). The CCSD(T)/aug-cc-pV5Z-PP combination results in values that are only 150 and 240 cm(-1) (<1% errors) removed from the experimental values for the (1)S → (3)D atomic transitions for Zn and Cd, respectively. Such spectroscopic constants provide the most accurate theoretical values known to date for bonding and photophysical parameters characteristic of Zn(n) and Cd(n) species.