Header

UZH-Logo

Maintenance Infos

Correlating infrared and X-ray absorption energies for molecular-level insight into hydrogen bond making and breaking in solution


Prémont-Schwarz, Mirabelle; Schreck, Simon; Iannuzzi, Marcella; Nibbering, Erik T J; Odelius, Michael; Wernet, Philippe (2015). Correlating infrared and X-ray absorption energies for molecular-level insight into hydrogen bond making and breaking in solution. Journal of Physical Chemistry B, 119(25):8115-8124.

Abstract

While ubiquitous, the making and breaking of hydrogen bonds in solution is notoriously difficult to study due to the associated complex changes of nuclear and electronic structures. With the aim to reduce the according uncertainty in correlating experimental observables and hydrogen-bond configurations, we combine the information from proximate methods to study the N–H···O hydrogen bond in solution. We investigate hydrogen-bonding of the N–H group of N-methylaniline with oxygen from liquid DMSO and acetone with infrared spectra in the N–H stretching region and X-ray absorption spectra at the N K-edge. We experimentally observe blue shifts of the infrared stretching band and an X-ray absorption pre-edge peak when going from DMSO to acetone. With ab initio molecular dynamics simulations and calculated spectra, we qualitatively reproduce the experimental observables but we do not reach quantitative agreement with experiment. The infrared spectra support the notion of weakening the N–H···O hydrogen bond from DMSO to acetone. However, we fail to theoretically reproduce the measured shift of the X-ray absorption pre-edge peak. We discuss possible shortcomings of the simulation models and spectrum calculations. Common features and distinct differences with the O–H···O hydrogen bond are highlighted, and the implications for monitoring hydrogen-bond breaking in solution are discussed.

Abstract

While ubiquitous, the making and breaking of hydrogen bonds in solution is notoriously difficult to study due to the associated complex changes of nuclear and electronic structures. With the aim to reduce the according uncertainty in correlating experimental observables and hydrogen-bond configurations, we combine the information from proximate methods to study the N–H···O hydrogen bond in solution. We investigate hydrogen-bonding of the N–H group of N-methylaniline with oxygen from liquid DMSO and acetone with infrared spectra in the N–H stretching region and X-ray absorption spectra at the N K-edge. We experimentally observe blue shifts of the infrared stretching band and an X-ray absorption pre-edge peak when going from DMSO to acetone. With ab initio molecular dynamics simulations and calculated spectra, we qualitatively reproduce the experimental observables but we do not reach quantitative agreement with experiment. The infrared spectra support the notion of weakening the N–H···O hydrogen bond from DMSO to acetone. However, we fail to theoretically reproduce the measured shift of the X-ray absorption pre-edge peak. We discuss possible shortcomings of the simulation models and spectrum calculations. Common features and distinct differences with the O–H···O hydrogen bond are highlighted, and the implications for monitoring hydrogen-bond breaking in solution are discussed.

Statistics

Citations

3 citations in Web of Science®
3 citations in Scopus®
Google Scholar™

Altmetrics

Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2015
Deposited On:21 Dec 2015 14:48
Last Modified:05 Apr 2016 19:30
Publisher:American Chemical Society (ACS)
ISSN:1520-5207
Publisher DOI:https://doi.org/10.1021/acs.jpcb.5b02954
PubMed ID:26029818

Download

Full text not available from this repository.
View at publisher

Article Networks

TrendTerms

TrendTerms displays relevant terms of the abstract of this publication and related documents on a map. The terms and their relations were extracted from ZORA using word statistics. Their timelines are taken from ZORA as well. The bubble size of a term is proportional to the number of documents where the term occurs. Red, orange, yellow and green colors are used for terms that occur in the current document; red indicates high interlinkedness of a term with other terms, orange, yellow and green decreasing interlinkedness. Blue is used for terms that have a relation with the terms in this document, but occur in other documents.
You can navigate and zoom the map. Mouse-hovering a term displays its timeline, clicking it yields the associated documents.

Author Collaborations