TY  - JOUR
A1  - Premont-Schwarz, Mirabelle
A1  - Schreck, Simon
A1  - Iannuzzi, Marcella
A1  - Nibbering, Erik T. J.
A1  - Odelius, Michael
A1  - Wernet, Philippe
T1  - Correlating Infrared and X-ray Absorption Energies for Molecular-Level Insight into Hydrogen Bond Making and Breaking in Solution
JF  - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry
N2  - 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 center dot center dot center dot 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 center dot center dot center dot 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 center dot center dot center dot O hydrogen bond are highlighted, and the implications for monitoring hydrogen-bond breaking in solution are discussed.
Y1  - 2015
U6  - https://doi.org/10.1021/acs.jpcb.5b02954
SN  - 1520-6106
VL  - 119
IS  - 25
SP  - 8115
EP  - 8124
PB  - American Chemical Society
CY  - Washington
ER  -