Guided ion beam and theoretical studies of the reactions of Re+, Os+, and Ir+ with CO

摘要

The kinetic-energy dependences of the reactions M+ + CO where M+ = Re+, Os+, and Ir+ are studied using guided ion-beam tandem mass spectrometry. Formation of both MO+ and MC+ was observed in endothermic processes for all three metals. Modeling of the data provides thresholds that yield 0K bond dissociation energies (BDEs, in eV) of 4.67 +/- 0.09 (Re+-O), 4.82 +/- 0.14 (Os+-O), 4.25 +/- 0.11 (Ir+-O), 5.13 +/- 0.12 (Re+-C), 6.14 +/- 0.14 (Os+-C), and 6.58 +/- 0.12 (Ir+-C). These BDEs agree well with literature values within experimental uncertainties demonstrating that ground state products are formed for all cases even though some of the reactions are formally spin forbidden. Quantum mechanical calculations at several levels of theory and using several basis sets were performed for MC+ and MO+ (with comparable results taken from the literature in some cases). B3LYP and CCSD(T) calculated ground state BDEs agree reasonably well with experimental values. The ground states in B3LYP and CCSD(T)/CBS calculations are (3)Sigma(-) (ReC+), (2)Delta(OsC+), and (1)Sigma(+) or (3)Delta (IrC+) after including spin-orbit considerations. Relaxed potential energy surfaces (PESs) for the M+ + CO reactions show crossings between surfaces of different spin states such that products can be formed with no barriers in excess of the substantial endothermicities. Unlike results for these metal cations reacting with O-2, the kinetic energy dependent cross sections for the formation of MO+ in the M+ + CO reactions exhibit only one feature. Reasons for this differential behavior are discussed in detail. Published by AIP Publishing.