Document Detail

Attaching molecular hydrogen to metal cations: perspectives from gas-phase infrared spectroscopy.
MedLine Citation:
PMID:  23034736     Owner:  NLM     Status:  Publisher    
In this perspective article we describe recent infrared spectroscopic investigations of mass-selected M(+)-H(2) and M(+)-D(2) complexes in the gas-phase, with targets that include Li(+)-H(2), B(+)-H(2), Na(+)-H(2), Mg(+)-H(2), Al(+)-H(2), Cr(+)-D(2), Mn(+)-H(2), Zn(+)-D(2) and Ag(+)-H(2). Interactions between molecular hydrogen and metal cations play a key role in several contexts, including in the storage of molecular hydrogen in zeolites, metal-organic frameworks, and doped carbon nanostructures. Arguably, the clearest view of the interaction between dihydrogen and a metal cation can be obtained by probing M(+)-H(2) complexes in the gas phase, free from the complicating influences of solvents or substrates. Infrared spectra of the complexes in the H-H and D-D stretch regions are obtained by monitoring M(+) photofragments as the excitation wavelength is scanned. The spectra, which feature full rotational resolution, confirm that the M(+)-H(2) complexes share a common T-shaped equilibrium structure, consisting essentially of a perturbed H(2) molecule attached to the metal cation, but that the structural and vibrational parameters vary over a considerable range, depending on the size and electronic structure of the metal cation. Correlations are established between intermolecular bond lengths, dissociation energies, and frequency shifts of the H-H stretch vibrational mode. Ultimately, the M(+)-H(2) and M(+)-D(2) infrared spectra provide a comprehensive set of benchmarks for modelling and understanding the M(+)H(2) interaction.
Viktoras Dryza; Berwyck L J Poad; Evan J Bieske
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-10-4
Journal Detail:
Title:  Physical chemistry chemical physics : PCCP     Volume:  -     ISSN:  1463-9084     ISO Abbreviation:  Phys Chem Chem Phys     Publication Date:  2012 Oct 
Date Detail:
Created Date:  2012-10-4     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  100888160     Medline TA:  Phys Chem Chem Phys     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
School of Chemistry, University of Melbourne, Melbourne, 3010, Australia.
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