Structural preferences, argon nanocoating, and dimerization of n-alkanols as revealed by OH stretching spectroscopy in supersonic jets.
n-Alkanols can occur in a multitude of energetically competitive conformational states. Using the OH stretching vibration as an infrared and Raman spectroscopic sensor in supersonic jet expansions, the torsional preferences around the Calpha-O and Cbeta-Calpha bonds are probed for n-propanol through n-hexanol. Raman detection is more powerful for isolated monomers, whereas IR spectroscopy is more sensitive for molecular complexes. The subtle IR vibrational shift induced by the nanocoating of n-alcohols with Ar atoms is shown to alternate with chain length. A large number of alcohol dimer absorptions is observed and subjected to collisional relaxation and nanocoating conditions. Essential features of the dimer spectra are modeled successfully by a simple force field approach. Exploratory quantum chemical calculations up to the MP2/aug-cc-pvqz level encourage a rigorous theoretical study of the subtle conformational aspects in monomers and possibly also in dimers of linear alcohols.
Wassermann
Tobias N
TN
Institut für Physikalische Chemie, Universität Göttingen, Tammannstrasse 6, 37077 Göttingen, Germany.
Zielke
Philipp
P
Lee
Juhyon J
JJ
Cézard
Christine
C
Suhm
Martin A
MA