Adsorption of Formamide at the Surface of Amorphous and Crystalline Ices under Interstellar and Tropospheric Conditions. A Grand Canonical Monte Carlo Simulation Study

Bálint Kiss, Sylvain Picaud, Milán Szöri, P. Jedlovszky

Research output: Article

Abstract

The adsorption of formamide is studied both at the surface of crystalline (I h ) ice at 200 K and at the surface of low density amorphous (LDA) ice in the temperature range of 50-200 K by grand canonical Monte Carlo (GCMC) simulation. These systems are characteristic of the upper troposphere and of the interstellar medium (ISM), respectively. Our results reveal that while no considerable amount of formamide is dissolved in the bulk ice phase in any case, the adsorption of formamide at the ice surface under these conditions is a very strongly preferred process, which has to be taken into account when studying the chemical reactivity in these environments. The adsorption is found to lead to the formation of multimolecular adsorption layer, the occurrence of which somewhat precedes the saturation of the first molecular layer. Due to the strong lateral interaction acting between the adsorbed formamide molecules, the adsorption isotherm does not follow the Langmuir shape. Adsorption is found to be slightly stronger on LDA than I h ice under identical thermodynamic conditions, due to the larger surface area exposed to the adsorption. Indeed, the monomolecular adsorption capacity of the LDA and I h ice surfaces is found to be 10.5 ± 0.7 μmol/m 2 and 9.4 μmol/m 2 , respectively. The first layer formamide molecules are very strongly bound to the ice surface, forming typically four hydrogen bonds with each other and the surface water molecules. The heat of adsorption at infinitely low surface coverage is found to be -105.6 kJ/mol on I h ice at 200 K.

Original languageEnglish
Pages (from-to)2935-2948
Number of pages14
JournalJournal of Physical Chemistry A
Volume123
Issue number13
DOIs
Publication statusPublished - ápr. 4 2019

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Ice
ice
Crystalline materials
Adsorption
adsorption
simulation
Molecules
Chemical reactivity
Troposphere
Monte Carlo simulation
formamide
molecules
Surface waters
Adsorption isotherms
troposphere
surface water
Hydrogen bonds
isotherms
Thermodynamics
reactivity

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "Adsorption of Formamide at the Surface of Amorphous and Crystalline Ices under Interstellar and Tropospheric Conditions. A Grand Canonical Monte Carlo Simulation Study",
abstract = "The adsorption of formamide is studied both at the surface of crystalline (I h ) ice at 200 K and at the surface of low density amorphous (LDA) ice in the temperature range of 50-200 K by grand canonical Monte Carlo (GCMC) simulation. These systems are characteristic of the upper troposphere and of the interstellar medium (ISM), respectively. Our results reveal that while no considerable amount of formamide is dissolved in the bulk ice phase in any case, the adsorption of formamide at the ice surface under these conditions is a very strongly preferred process, which has to be taken into account when studying the chemical reactivity in these environments. The adsorption is found to lead to the formation of multimolecular adsorption layer, the occurrence of which somewhat precedes the saturation of the first molecular layer. Due to the strong lateral interaction acting between the adsorbed formamide molecules, the adsorption isotherm does not follow the Langmuir shape. Adsorption is found to be slightly stronger on LDA than I h ice under identical thermodynamic conditions, due to the larger surface area exposed to the adsorption. Indeed, the monomolecular adsorption capacity of the LDA and I h ice surfaces is found to be 10.5 ± 0.7 μmol/m 2 and 9.4 μmol/m 2 , respectively. The first layer formamide molecules are very strongly bound to the ice surface, forming typically four hydrogen bonds with each other and the surface water molecules. The heat of adsorption at infinitely low surface coverage is found to be -105.6 kJ/mol on I h ice at 200 K.",
author = "B{\'a}lint Kiss and Sylvain Picaud and Mil{\'a}n Sz{\"o}ri and P. Jedlovszky",
year = "2019",
month = "4",
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doi = "10.1021/acs.jpca.9b00850",
language = "English",
volume = "123",
pages = "2935--2948",
journal = "Journal of Physical Chemistry A",
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publisher = "American Chemical Society",
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TY - JOUR

T1 - Adsorption of Formamide at the Surface of Amorphous and Crystalline Ices under Interstellar and Tropospheric Conditions. A Grand Canonical Monte Carlo Simulation Study

AU - Kiss, Bálint

AU - Picaud, Sylvain

AU - Szöri, Milán

AU - Jedlovszky, P.

PY - 2019/4/4

Y1 - 2019/4/4

N2 - The adsorption of formamide is studied both at the surface of crystalline (I h ) ice at 200 K and at the surface of low density amorphous (LDA) ice in the temperature range of 50-200 K by grand canonical Monte Carlo (GCMC) simulation. These systems are characteristic of the upper troposphere and of the interstellar medium (ISM), respectively. Our results reveal that while no considerable amount of formamide is dissolved in the bulk ice phase in any case, the adsorption of formamide at the ice surface under these conditions is a very strongly preferred process, which has to be taken into account when studying the chemical reactivity in these environments. The adsorption is found to lead to the formation of multimolecular adsorption layer, the occurrence of which somewhat precedes the saturation of the first molecular layer. Due to the strong lateral interaction acting between the adsorbed formamide molecules, the adsorption isotherm does not follow the Langmuir shape. Adsorption is found to be slightly stronger on LDA than I h ice under identical thermodynamic conditions, due to the larger surface area exposed to the adsorption. Indeed, the monomolecular adsorption capacity of the LDA and I h ice surfaces is found to be 10.5 ± 0.7 μmol/m 2 and 9.4 μmol/m 2 , respectively. The first layer formamide molecules are very strongly bound to the ice surface, forming typically four hydrogen bonds with each other and the surface water molecules. The heat of adsorption at infinitely low surface coverage is found to be -105.6 kJ/mol on I h ice at 200 K.

AB - The adsorption of formamide is studied both at the surface of crystalline (I h ) ice at 200 K and at the surface of low density amorphous (LDA) ice in the temperature range of 50-200 K by grand canonical Monte Carlo (GCMC) simulation. These systems are characteristic of the upper troposphere and of the interstellar medium (ISM), respectively. Our results reveal that while no considerable amount of formamide is dissolved in the bulk ice phase in any case, the adsorption of formamide at the ice surface under these conditions is a very strongly preferred process, which has to be taken into account when studying the chemical reactivity in these environments. The adsorption is found to lead to the formation of multimolecular adsorption layer, the occurrence of which somewhat precedes the saturation of the first molecular layer. Due to the strong lateral interaction acting between the adsorbed formamide molecules, the adsorption isotherm does not follow the Langmuir shape. Adsorption is found to be slightly stronger on LDA than I h ice under identical thermodynamic conditions, due to the larger surface area exposed to the adsorption. Indeed, the monomolecular adsorption capacity of the LDA and I h ice surfaces is found to be 10.5 ± 0.7 μmol/m 2 and 9.4 μmol/m 2 , respectively. The first layer formamide molecules are very strongly bound to the ice surface, forming typically four hydrogen bonds with each other and the surface water molecules. The heat of adsorption at infinitely low surface coverage is found to be -105.6 kJ/mol on I h ice at 200 K.

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