Investigations of strong hydrogen bonding in (ROH)n...FHF- (n = 1, 2 and R = H, CH3, C2H5) clusters via high-pressure mass spectrometry and quantum calculations.
An examination of strong hydrogen bonds found in (ROH)(n)...FHF(-) clusters (n = 1 and 2; R = H, CH(3), C(2)H(5)) is presented. Excellent agreement is observed between thermochemical values obtained from high-pressure mass spectrometric measurements and those predicted from MP2(full)/6-311++G(d,p)//B3LYP/6-311++G(d,p) calculations. Calculated structures are examined, and insight into the geometric nature of the bonding for these systems is obtained. In the case of water binding to FHF(-), it was found that the large entropic advantage of one particular structure, which was not the most enthalpically favored, was significant enough to make it the predominant species within the ion source. In the case of methanol solvation, no evidence of secondary interaction of the methyl group and any other moiety could be found. The structural details revealed from calculations of the ethanol-solvated clusters indicate that secondary interactions between the terminal methyl group and FHF(-) have an impact on the length of the FHF and OHF bonds.
Nieckarz
Robert J
RJ
Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada.
Oldridge
Nathan
N
Fridgen
Travis D
TD
Li
Guanping P
GP
Hamilton
Ian P
IP
McMahon
Terry B
TB
D000438:Alcohols / Q000737:chemistry*; D005461:Fluorine / Q000737:chemistry*; D005740:Gases / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D013058:Mass Spectrometry; D008958:Models, Molecular; D008968:Molecular Conformation; D011312:Pressure; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry; D013696:Temperature; D014867:Water / Q000737:chemistry*
D000438:Alcohols; D005740:Gases; D012997:Solvents; D014867:Water; D005461:Fluorine; D006859:Hydrogen