Ligand effects in gold-carbonyl complexes: Evaluation of the bond dissociation energies using blackbody infrared radiative dissociation

In a previous work, the ability of gold-carbonyl bond dissociation energies (BDEs) to describe ligand effects in gold(I) complexes was probed using collision-induced measurements. Despite large experimental error technique, results agreed with theoretical description these effects. We propose here another approach evaluate BDEs [LAu-CO]+ complexes, by Blackbody Infrared Radiative Dissociation (BIRD) method which is able provide absolute energetic To this aim, 8 studied obtain their Arrhenius activation energies. Because do not reach rapid energy exchange (REX) limit conditions, critical dissociations were then determined kinetic data and an Equilibrium Truncated Thermal (ETT) internal distribution model implemented RRKM-QET MassKinetics software. validate our approach, known proton-bound amino acid dimers first reinvestigated model. The are excellent agreement those reported literature. This indicates that assumptions simple reasonable allow determination accurate For even though shift (from 0.18 0.26 eV) observed between binding obtained calculated values, linear tendency two sets still obtained. These use BIRD combination equilibrium truncated thermal distributions for relatively small ions. It also shown herein measure good descriptor may be reliably evaluated technique.