Adsorption of acetaldehyde on ice as seen from computer simulation and infrared spectroscopy measurements

Mária Darvas, Jérôme Lasne, Carine Laffon, Philippe Parent, Sylvain Picaud, P. Jedlovszky

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

Detailed investigation of the adsorption of acetaldehyde on I h ice is performed under tropospheric conditions by means of grand canonical Monte Carlo computer simulations and compared to infrared spectroscopy measurements. The experimental and simulation results are in a clear accordance with each other. The simulations indicate that the adsorption process follows Langmuir behavior in the entire pressure range of the vapor phase of acetaldehyde. Further, it was found that the adsorption layer is strictly monomolecular, and the adsorbed acetaldehyde molecules are bound to the ice surface by only one hydrogen bond, typically formed with the dangling H atoms at the ice surface, in agreement with the experimental results. Besides this hydrogen bonding, at high surface coverages dipolar attraction between neighboring acetaldehyde molecules also contributes considerably to the energy gain of the adsorption. The acetaldehyde molecules adopt strongly tilted orientations relative to the ice surface, the tilt angle being scattered between 50° and 90° (i.e., perpendicular orientation). The range of the preferred tilt angles narrows, and the preference for perpendicular orientation becomes stronger upon saturation of the adsorption layer. The CH 3 group of the acetaldehyde molecules points as straight away from the ice surface within the constraint imposed by the tilt angle adopted by the molecule as possible. The heat of adsorption at infinitely low coverage is found to be -36 ± 2 kJ/mol from the infrared spectroscopy measurement, which is in excellent agreement with the computer simulation value of -34.1 kJ/mol.

Original languageEnglish
Pages (from-to)4198-4207
Number of pages10
JournalLangmuir
Volume28
Issue number9
DOIs
Publication statusPublished - Mar 6 2012

Fingerprint

Acetaldehyde
acetaldehyde
Ice
Infrared spectroscopy
ice
computerized simulation
infrared spectroscopy
Adsorption
adsorption
Computer simulation
Molecules
spectroscopy
molecules
Hydrogen bonds
attraction
simulation
Vapors
methylidyne
vapor phases
hydrogen bonds

ASJC Scopus subject areas

  • Electrochemistry
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Materials Science(all)
  • Spectroscopy

Cite this

Adsorption of acetaldehyde on ice as seen from computer simulation and infrared spectroscopy measurements. / Darvas, Mária; Lasne, Jérôme; Laffon, Carine; Parent, Philippe; Picaud, Sylvain; Jedlovszky, P.

In: Langmuir, Vol. 28, No. 9, 06.03.2012, p. 4198-4207.

Research output: Contribution to journalArticle

Darvas, Mária ; Lasne, Jérôme ; Laffon, Carine ; Parent, Philippe ; Picaud, Sylvain ; Jedlovszky, P. / Adsorption of acetaldehyde on ice as seen from computer simulation and infrared spectroscopy measurements. In: Langmuir. 2012 ; Vol. 28, No. 9. pp. 4198-4207.
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