Interactions of CHCl3 molecules with a crystalline ice grown on Pt(111) studied by metastable impact electron spectroscopy

Aoki, Masaru; Ohashi, Yusuke; Masuda, S.

doi:10.1016/s0039-6028(03)00127-4

Cited by 14 publications

(21 citation statements)

References 15 publications

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“…A similar result was obtained later by Pysanenko et al considering CH 3 Cl molecules adsorbed on ice, who concluded that the interaction with the polar water molecules inhibits the mobility of the adsorbed molecules. 20 Moreover, it was also shown by means of metastable impact electron spectroscopy that CHCl 3 molecules are adsorbed at the ice surface with their H atom oriented towards the substrate below 120 K, 21 and for all chlorinated methane derivatives (CH 4-x Cl x ) that their interaction with water occurs through the oxygen atom. 22 Finally, Vysokikh et al…”

Section: Introductionmentioning

confidence: 99%

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

2017

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The adsorption behavior of three chlorinated methane derivative molecules, namely CH 3 Cl, CHCl 3 , and CCl 4 is investigated at the (0001) surface of I h 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 CH 4 , CH 2 Cl 2 , and fluorinated methane derivatives. Our results show that neither CHCl 3 nor CCl 4 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, CH 3 Cl does exhibit noticeable adsorption on ice, and the adsorbed molecules prefer to turn towards 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 analogs, 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 analogs, which prevents the formation or completion of the adsorption layer of the chlorinated molecules.

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Section: Introductionmentioning

confidence: 99%

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

2017

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“…These studies led to the conclusion that there is a marked difference between monolayer and multilayer adsorption states of CHCl 3 at the surface of crystalline ice, but no such difference is seen at amorphous ice [24,25]. Aoki et al showed, using metastable impact electron spectroscopy that CH 3 Cl molecules adsorbed at the ice surface turn their H atoms towards the ice phase below 120 K [26]. It was also shown that both CHCl 3 [24,25] and CH 3 Cl [27] remain immobile at the ice surface in the entire temperature range below desorption due to their interaction with the surface water molecules [24,25,27], and that the interaction of all chlorinated methane derivatives with water involves the water O atom [28].…”

Section: Introductionmentioning

confidence: 99%

Dependence of the adsorption of halogenated methane derivatives at the ice surface on their chemical structure

Sumi

Picaud

Jedlovszky

2017

Journal of Molecular Liquids

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The adsorption of all the fluorinated and chlorinated methane derivatives as well as methane itself at the surface of I h ice is studied at the tropospheric temperature of 200 K by grand canonical Monte Carlo simulations. The general behaviour of the obtained isotherms is in good accordance with existing experimental data, giving us confidence in the models used. The shape of the adsorption isotherms is discussed in terms of the interplay of adhesive and cohesive interactions. It is found that in cases when the former of the two interactions is clearly the stronger one, multilayer adsorption occurs; when the latter interaction is the dominant one, no considerable adsorption is observed, while in cases when the two interactions are of roughly the same strength, the formation of a saturated monolayer occurs. The isotherms exhibit the Langmuir shape, at least up to the pressures where multilayer adsorption starts to occur, given that the cohesion acting between the adsorbate molecules is only moderately strong. Too strong cohesion, on the other hand, leads to the deviation of the isotherm from the Langmuir shape. While the strength of cohesion depends on the properties of the adsorbate molecules, that of adhesion is determined by hydrogen bond formation between the adsorbed molecules and surface waters. Our results show that while CH 3 F and CH 3 Cl form several weak, C-H donated hydrogen bonds with the surface molecules of the ice phase, the adsorbates containing more than one halogen atom form only one, though strong, O-H donated hydrogen bond with them.

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“…These studies report the experimental investigation of the molecular structure and bonding of water at the chloroformwater interface using vibrational sum-frequency spectroscopy (VSFS). Although there have been studies investigating chloroform adsorbed on ice or in vacuum, [23][24][25] a detailed experimental study of the condensed fluid phase chloroformwater interface has yet to be carried out to our knowledge. By examining the OH stretch modes of the interfacial water molecules, different types of hydrogen-bonded water species can be discerned and characterized with regards to their interfacial structuring.…”

Section: Introductionmentioning

confidence: 99%

The Unique Molecular Behavior of Water at the Chloroform—Water Interface

McFearin

Richmond

2010

Appl Spectrosc

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The molecular bonding and orientation of water at the chloroform-water interface has been examined in this study using vibrational sum-frequency spectroscopy (VSFS). The results provide a key puzzle piece towards our understanding of the systematic changes in the interfacial bonding and orientation of water that occur with variations in the polarity of the organic phase, especially when compared with previous studies of different liquid-liquid interfacial systems. In these VSFS studies the OH spectral responses of interfacial water molecules are used to characterize the interactions between water and the organic phase. The spectral analysis, aided by isotopic dilution studies, shows that the moderate polarity of the chloroform phase results in a mixed interfacial region with stronger organic-water bonding and fewer bonding interactions between adjacent water molecules than was previously found for studies of non-polar organic liquid-water interfaces. Even with the more mixed interfacial region and stronger organic-water interactions, interfacial water retains a significant amount of orientational ordering. These results are compared with recent predictions from molecular dynamics simulations about how molecules behave at the chloroform-water interface.

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Interactions of CHCl3 molecules with a crystalline ice grown on Pt(111) studied by metastable impact electron spectroscopy

Cited by 14 publications

References 15 publications

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

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

Dependence of the adsorption of halogenated methane derivatives at the ice surface on their chemical structure

The Unique Molecular Behavior of Water at the Chloroform—Water Interface

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