Adsorption of Chlorinated Methane Derivatives at the Ice Surface: A Grand Canonical Monte Carlo Simulation Study

Ildikó Sumi, Sylvain Picaud, P. Jedlovszky

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The adsorption behavior of three chlorinated methane derivative molecules, CH3Cl, CHCl3, and CCl4, is investigated at the (0001) surface of Ih ice at the tropospheric temperature of 200 K by means of grand canonical Monte Carlo simulations. This study completes our earlier investigations concerning the adsorption of CH4, CH2Cl2, and fluorinated methane derivatives. Our results show that neither CHCl3 nor CCl4 exhibits any adsorption. This complete lack of adsorption is attributed to the interplay of the very strong cohesion acting between the adsorbate molecules, and their relatively weak interaction with the ice phase. By contrast, CH3Cl does exhibit a noticeable adsorption on ice, and the adsorbed molecules prefer to turn toward the ice surface by their H atoms, forming weak, C-H⋯·O-type hydrogen bonds with surface waters. The lateral (i.e., adsorbate-adsorbate) contribution to the total interaction energy of the adsorbed molecules is always considerably larger (in magnitude) than in the case of the corresponding fluorinated analogues, making also the total adsorption energy lower for the chlorinated molecules than for their fluorinated counterpart. As a consequence of this strong attraction between the chlorinated adsorbate molecules, their condensation occurs at lower chemical potential (and, hence, pressure) values than that of the fluorinated analogues, which prevents the formation or completion of the adsorption layer of the chlorinated molecules.

Original languageEnglish
Pages (from-to)7782-7793
Number of pages12
JournalJournal of Physical Chemistry C
Volume121
Issue number14
DOIs
Publication statusPublished - Apr 13 2017

Fingerprint

Methane
Ice
ice
methane
Derivatives
Adsorption
Molecules
adsorption
Adsorbates
molecules
simulation
analogs
cohesion
Chemical potential
Monte Carlo simulation
surface water
Surface waters
attraction
Condensation
Hydrogen bonds

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Adsorption of Chlorinated Methane Derivatives at the Ice Surface : A Grand Canonical Monte Carlo Simulation Study. / Sumi, Ildikó; Picaud, Sylvain; Jedlovszky, P.

In: Journal of Physical Chemistry C, Vol. 121, No. 14, 13.04.2017, p. 7782-7793.

Research output: Contribution to journalArticle

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N2 - The adsorption behavior of three chlorinated methane derivative molecules, CH3Cl, CHCl3, and CCl4, is investigated at the (0001) surface of Ih ice at the tropospheric temperature of 200 K by means of grand canonical Monte Carlo simulations. This study completes our earlier investigations concerning the adsorption of CH4, CH2Cl2, and fluorinated methane derivatives. Our results show that neither CHCl3 nor CCl4 exhibits any adsorption. This complete lack of adsorption is attributed to the interplay of the very strong cohesion acting between the adsorbate molecules, and their relatively weak interaction with the ice phase. By contrast, CH3Cl does exhibit a noticeable adsorption on ice, and the adsorbed molecules prefer to turn toward the ice surface by their H atoms, forming weak, C-H⋯·O-type hydrogen bonds with surface waters. The lateral (i.e., adsorbate-adsorbate) contribution to the total interaction energy of the adsorbed molecules is always considerably larger (in magnitude) than in the case of the corresponding fluorinated analogues, making also the total adsorption energy lower for the chlorinated molecules than for their fluorinated counterpart. As a consequence of this strong attraction between the chlorinated adsorbate molecules, their condensation occurs at lower chemical potential (and, hence, pressure) values than that of the fluorinated analogues, which prevents the formation or completion of the adsorption layer of the chlorinated molecules.

AB - The adsorption behavior of three chlorinated methane derivative molecules, CH3Cl, CHCl3, and CCl4, is investigated at the (0001) surface of Ih ice at the tropospheric temperature of 200 K by means of grand canonical Monte Carlo simulations. This study completes our earlier investigations concerning the adsorption of CH4, CH2Cl2, and fluorinated methane derivatives. Our results show that neither CHCl3 nor CCl4 exhibits any adsorption. This complete lack of adsorption is attributed to the interplay of the very strong cohesion acting between the adsorbate molecules, and their relatively weak interaction with the ice phase. By contrast, CH3Cl does exhibit a noticeable adsorption on ice, and the adsorbed molecules prefer to turn toward the ice surface by their H atoms, forming weak, C-H⋯·O-type hydrogen bonds with surface waters. The lateral (i.e., adsorbate-adsorbate) contribution to the total interaction energy of the adsorbed molecules is always considerably larger (in magnitude) than in the case of the corresponding fluorinated analogues, making also the total adsorption energy lower for the chlorinated molecules than for their fluorinated counterpart. As a consequence of this strong attraction between the chlorinated adsorbate molecules, their condensation occurs at lower chemical potential (and, hence, pressure) values than that of the fluorinated analogues, which prevents the formation or completion of the adsorption layer of the chlorinated molecules.

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