Theoretical study of the electronic spectrum of binuclear gold(I) complexes

The electronic structure and the spectroscopic properties of [Au 2 (CS 3 ) 2 ] −2 , [Au 2 (pym‐2‐S) 2 ] (pym = pyrimidethiolate), [Au 2 (dpm) 2 ] +2 (dpm = bis(diphosphino)methane) were studied using density functional theory (DFT) at the B3LYP level. The absorption spectrum of these binuclear gold(I) complexes was calculated by single excitation time‐dependent (TD) method. All complexes showed a 1 (5 d σ* → 6 p σ) transition associated with a metal–metal charge transfer, which is strongly interrelated with the gold–gold distance. Furthermore, we have calculated the frequency of the gold–gold vibration (ν Au2 ) on the above complexes. The values obtained are theoretically in agreement with experimental range. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005