The bond energy of Rh2

Abstract

In a spectroscopic investigation of jet-cooled Rh2 by the resonant two-photon ionization method, an abrupt predissociation threshold is observed in a dense set of vibronic levels at 19 405±4 cm−1. Based on the high density of states expected in the rhodium dimer, the sharp definition of the predissociation threshold that is observed, and the validation of a similar conclusion in the case of V2, it is argued that predissociation occurs as soon as the energy of the separated ground state atoms is exceeded. On this basis the bond energy of Rh2 is assigned as D0(Rh2)=19 405±4 cm−1=2.4059±0.0005 eV. This value is compared to the results of other experiments and to theoretical calculations. The bond energy of disilver, D0(Ag2)=1.65±0.03 eV, provides a particularly useful standard of comparison, and suggests that 4d contributions to the bond energy of Rh2 amount to at least 0.76 eV.

Investigation of the use of density functionals in second‐ and third‐row transition metal dimer calculations

“…By taking 400,000 electronic configurations into account, CASSCF followed by MRCI (CASSCF/MRCI) method 41 42 and ω e = 283.9±1.8 cm −1 . 43 Calculated MP2 results are thus inaccurate.…”

Probing the structures of gas-phase rhodium cluster cations by far-infrared spectroscopy

“…Spectroscopic investigations of rhodium clusters, which can provide experimental details of their structure, are limited. The stretching frequency 29 and bond dissociation energy 30 of the dimer have been measured, while electron spin resonance spectroscopy determined the trimer to have D 3h symmetry. 31 We have recently reported a combined far-infrared multiple photon dissociation (FIR-MPD) spectroscopy and DFT study of Rh + 8 , from which we determined the structure to be a bicapped octahedron (bc-oh).…”

Interaction of MSn (MRu, Rh, Pd) dimers with CH2 and CF2: A density functional study

“…The high‐level multi‐reference self‐consistent‐field configuration interaction (MRSCFCI) ab initio calculation predicted RhRh binding energy of 46.1 kcal · mol −1 that is about 13.1 kcal · mol −1 higher in energy than our predicted value. Two different experimental studies estimated the RhRh binding energy to be 56.8 and 32.3 kcal · mol −1 34, 35. Recently, the reactivity of the Rh clusters and its relation to the magnetism and topology were studied theoretically 36, 37.…”