Change search
ReferencesLink to record
Permanent link

Direct link
Blue-shifting hydrogen bonds
KTH, Superseded Departments, Biotechnology.
2002 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 106, no 18, 4695-4702 p.Article in journal (Refereed) Published
Abstract [en]

In this paper we put forward the idea that the various improper, blue-shifting hydrogen bond systems discussed in the literature are all of essentially the same nature and occur because of three necessary circumstances: (i) the presence of a negative dipole moment derivative, dmu(0)/dr(XH), for the isolated H-bond donor molecule; (ii) the interaction between such a molecule and any electron density concentration on the H-bond acceptor ( pi-system density, lone-pair density, ionic charge,...) which at large intermolecular distances gives rise to a field-dominated, modest vibrational blue shift; (iii) an additional blue shift due to electronic exchange overlap. The negative dipole moment derivative is a necessary but not sufficient condition for the formation of a blue-shifted H-bond: thus, the blue-shifting CH4, F3CH, and Cl3CH molecules and their relatives can also give rise to normal, red-shifted H-bonds. This is a logical extension of the blue-shifting property and occurs when the electric field from the acceptor is sufficiently strong at the intermolecular equilibrium distance (e.g., for F- and Cl- acceptors).

Place, publisher, year, edition, pages
2002. Vol. 106, no 18, 4695-4702 p.
Keyword [en]
vibrational frequency, electric-field, abinitio calculations, solid hydroxides, oh frequency, spectra, co, fluorobenzene, cluster, dimer
URN: urn:nbn:se:kth:diva-21529ISI: 000175488400032OAI: diva2:340227
QC 20100525Available from: 2010-08-10 Created: 2010-08-10Bibliographically approved

Open Access in DiVA

No full text

Search in DiVA

By author/editor
Hermansson, Kersti
By organisation
In the same journal
Journal of Physical Chemistry A

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Total: 35 hits
ReferencesLink to record
Permanent link

Direct link