Publication Type |
Journal Article |
School or College |
College of Science |
Department |
Chemistry |
Creator |
Armentrout, Peter B. |
Other Author |
Hinton, Christopher S. |
Title |
Guided ion beam and theoretical study of the reactions of Hf+ with H2, D2, and HD |
Date |
2010-01-01 |
Description |
The kinetic energy dependences of reactions of the third-row transition metal cation Hf+ with H2, D2, and HD were determined using a guided ion beam tandem mass spectrometer. A flow tube ion source produces Hf+ in its 2D (6s25d1) electronic ground state level. Corresponding state-specific reaction cross sections are obtained. The kinetic energy dependences of the cross sections for the endothermic formation of HfH+ and HfD+ are analyzed to give a 0 K bond dissociation energy of D0 (Hf+-H)=2.11±0.08 eV. Quantum chemical calculations at several levels of theory performed here generally overestimate the experimental bond energy but results obtained using the Becke-half-and-half-LYP functional show good agreement. Theory also provides the electronic structures of these species and the reactive potential energy surfaces. Results from the reactions with HD provide insight into the reaction mechanisms and indicates that Hf+ reacts via a statistical mechanism. We also compare this third-row transition metal system with the first-row and second-row congeners, Ti+ and Zr+, and find that Hf+ has a weaker M+-H bond. As most third-row transition metal hydride cation bonds exceed their lighter congeners, this trend is unusual but can be understood using promotion energy arguments. |
Type |
Text |
Publisher |
American Institute of Physics (AIP) |
Volume |
133 |
Issue |
12 |
First Page |
124307-1 |
Last Page |
124307-10 |
DOI |
doi:10.1063/1.3482663 |
Dissertation Institution |
University of Utah |
Language |
eng |
Bibliographic Citation |
Hinton, C. S., & Armentrout, P. B. (2010). Guided ion beam and theoretical study of the reactions of Hf+ with H2, D2, and HD. Journal of Chemical Physics, 133(12), 124307-1-10. |
Rights Management |
(c)American Institute of Physics. The following article appeared in (c)American Institute of Physics. The following article appeared in Hinton, C. S., & Armentrout, P. B. (2010). Guided ion beam and theoretical study of the reactions of Hf+ with H2, D2, and HD. Journal of Chemical Physics, 133 (12), art. no. 124307 and may be found at (http://www.ncbi.nlm.nih.gov/pubmed/20886932). |
Format Medium |
application/pdf |
Format Extent |
409,910 bytes |
Identifier |
uspace,14803 |
ARK |
ark:/87278/s68s57kb |
Setname |
ir_uspace |
ID |
707569 |
Reference URL |
https://collections.lib.utah.edu/ark:/87278/s68s57kb |