
doi: 10.1002/jcc.23678
pmid: 25043253
By performing MP2/aug‐cc‐pVTZab initiocalculations for a large set of dimer systems possessing a RH hydridic bond involved in diverse types of intermolecular interactions (dihydrogen bonds, hydride halogen bonds, hydride hydrogen bonds, and charge‐assisted hydride hydrogen bonds), we show that this is rather an elongation than a shortening that a hydride bond undergoes on interaction. Contrary to what might have been expected on the basis of studies in uniform electric field, this elongation is accompanied by a blue instead of red shift of the RH stretching vibration frequency. We propose that the “additional” elongation of the RH hydridic bond results from the significant charge outflow from the sigma bonding orbital of RH that weakens this bond. The more standard red shift obtained for stronger complexes is explained by means of the Hermansson's formula and the particularly strong electric field produced by the H‐acceptor molecule. © 2014 Wiley Periodicals, Inc.
| selected citations These citations are derived from selected sources. This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically). | 22 | |
| popularity This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network. | Top 10% | |
| influence This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically). | Average | |
| impulse This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network. | Top 10% |
