Systematic effect of d substitution on hydrogen-bond lengths in gas-phase dimers B…HX and a model for its interpretation

✍ Scribed by A.C. Legon; D.J. Millen

• Publisher: Elsevier Science
• Year: 1988
• Tongue: English
• Weight: 602 KB
• Volume: 147
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(88)85013-9

✦ Synopsis

The hydrogen-bond lengths r( B...H-X) and r(B...D-X) have been redetermined on a consistent basis for the axially symmetric dimers B...HX, where B=N2, CO, PHa, HCN, CHsCN, NH,, or (CH3)3N and X=F, Cl or CN. For the series B...HF and B...HCl, the difference in the effective zero-point bond lengths Sr=r(B...H-X) -r(B...D-X) is found to decrease as the hydrogen bond strength ($) increases. This behaviour is interpreted in terms of the effect of D substitution on the opposing contributions to the zero-point motion of the two modes ( vs and ve) that involve large-amplitude displacements of the H atom.