Samarium cation (Sm+) reactions with H2, D2, and HD: SmH+ bond energy and mechanistic insights from guided ion beam and theoretical studies
Abstract
Guided ion beam tandem mass spectrometry is used to study the reaction of the lanthanide samarium cation (Sm+) with H2 and its isotopologues (HD and D2) as a function of collision energy. Modeling the resulting energy dependent product ion cross sections from these endothermic reactions yields 2.03 ± 0.06 eV (two standard deviations) for the 0 K bond dissociation energy of SmH+. Quantum chemical calculations are performed to determine stabilities of the ground and low-energy states of SmH+ for comparison with the experimentally measured thermochemistry. The calculations generally overestimate the SmH+ bond energy, but a better agreement between experiment and theory is achieved after correcting for spin-orbit energy contributions, with coupled-cluster with single, double and perturbative triple excitations/complete basis set [CCSD(T)/CBS] results reproducing the experiment well. In the HD reaction, the SmH+ product is observed to be favored over the SmD+ by about a factor of three, indicating that the reaction proceeds via a direct mechanism with short-lived intermediates. This is consistent with quantum chemical calculations of relaxed potential energy surface scans of SmH2+, which show that there is no strongly bound dihydride intermediate. The reactivity and hydride bond energy of Sm+, which has a valence electron configuration typical of most lanthanides, are compared with previous results for the lanthanide cations La+, Gd+, and Lu+, which exhibit configurations more closely related to the group 3 metal cations, Sc+ and Y+. Periodic trends across the lanthanide series and insights into the role of the electronic configurations on hydride bond strength and reactivity with H2 are discussed.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Oct 25, 2018
- Source ID
- 10.1063/1.5053758
Entities
People
- Maria Demireva
- Peter Armentrout
Organizations
- Air Force Office of Scientific Research
- University of Utah