Origin of the Argon Nanocoating Shift in the OH Stretching Fundamental of n-Propanol: A Combined Experimental and Quantum Chemical Study
| Autor: | Martin A. Suhm, Juhyon J. Lee, Sebastian Höfener, Tobias N. Wassermann, Wim Klopper |
|---|---|
| Rok vydání: | 2009 |
| Předmět: |
Jet (fluid)
Argon 010304 chemical physics Analytical chemistry Solvation chemistry.chemical_element 010402 general chemistry 01 natural sciences 0104 chemical sciences Surfaces Coatings and Films Electronic Optical and Magnetic Materials Vibration Propanol chemistry.chemical_compound symbols.namesake General Energy chemistry Chemical physics 0103 physical sciences Bathochromic shift symbols Molecule Physical and Theoretical Chemistry Raman spectroscopy |
| Zdroj: | The Journal of Physical Chemistry C. 113:10929-10938 |
| ISSN: | 1932-7455 1932-7447 |
| DOI: | 10.1021/jp902194h |
| Popis: | Supersonic jet Raman spectroscopy reveals an increasing bathochromic shift of the OH stretching vibration in the most stable conformation of propanol with increasing extent of argon nanocoating. It falls short of the bulk matrix limit of 17 cm−1 even at large nozzle distances. Quantum chemical harmonic frequency calculations up to the CCSD(T) level show that this shift cannot be accounted for by individual Ar atoms or even a first solvation layer but instead requires several layers of Ar atoms around the molecule to be explained. It is shown that the stability of Ar−propanol clusters correlates with the number of close O and C contacts to the Ar and that bathochromic shifts are largely caused by backbone solvation. Hydrogen-bonding OH solvation tends to slightly increase the OH stretching frequency but is very sensitive to the computational level. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|