Quantum study of the adsorption of small molecules on ice: The infrared frequency of the surface hydroxyl group and the vibrational stark effect

Manca, Carine; Allouche, A.

doi:10.1063/1.1331106

Cited by 33 publications

(37 citation statements)

References 55 publications

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“…From an analysis of the spectra shown in Figs 1(a)–(d), three distinct vibrational frequencies for CO on and in H 2 O environments can be identified; one at 2152 cm −1 , one at 2139 cm −1 and (at higher temperatures) one at 2136 cm −1 . In combination with the results of previous experimental and theoretical work (Al‐Halabi, van Dishoeck & Kroes 2004; Al‐Halabi et al 2003, 2004; Collings et al 2002, 2003a,b; Devlin 1992; Manca, Roubin & Martin 2000; Manca & Allouche 2001; Manca et al 2001), these features have be associated with various binding sites for CO on and in H 2 O environments, as summarized in Fig. 2.…”

Section: Experimental Results From Layered Co–h2o Icessupporting

confidence: 70%

Using laboratory studies of CO-H₂O ices to understand the non-detection of a 2152 cm⁻¹(4.647 μm) band in the spectra of interstellar ices

Fraser

Collings

Dever

et al. 2004

Monthly Notices of the Royal Astronomical Society

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We present results from laboratory experiments on layered CO-H 2 O-ice systems, carried out from sub-monolayer to multilayer CO coverages, and review recent experimental data, as published by the authors. Under certain specific laboratory conditions the 2152 cm −1 feature, associated with CO molecules adsorbed at dangling-OH bonds at the ice surface, is 'missing'. A detailed analysis is used to understand why the same feature is not detected in spectra of interstellar ices. We conclude that the dangling-OH sites do exist in interstellar ices but that the sites are blocked by another species. The astronomical implications of this deduction are discussed.

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Section: Experimental Results From Layered Co–h2o Icessupporting

confidence: 70%

Using laboratory studies of CO-H₂O ices to understand the non-detection of a 2152 cm⁻¹(4.647 μm) band in the spectra of interstellar ices

Fraser

Collings

Dever

et al. 2004

Monthly Notices of the Royal Astronomical Society

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“…[1][2][3][4][5] Infrared spectroscopy revealed the signature of the organisation of the ASW surface: two weak absorption bands, observed at the base of the blue wing of the bulk OH stretching absorption band, were attributed to free OH oscillators ''dangling'' from the ice surface. [1][2][3][4][5] Infrared spectroscopy revealed the signature of the organisation of the ASW surface: two weak absorption bands, observed at the base of the blue wing of the bulk OH stretching absorption band, were attributed to free OH oscillators ''dangling'' from the ice surface.…”

Section: Introductionmentioning

confidence: 99%

Inhomogeneity of the amorphous solid water dangling bonds

Coussan

Roubin

Noble

2015

Phys. Chem. Chem. Phys.

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Amorphous solid water (ASW) is one of the most widely studied molecular systems because of its importance in the physics and chemistry of the interstellar medium and the upper layers of the Earth's atmosphere. Although the global structure of this material, i.e. the bulk and the surface, is well characterised, we are far from having an overall understanding of the changes induced upon chemical or physical perturbation. More specifically, the behaviour of the surface and the immediate sublayers upon mid-infrared irradiation must be understood due to its direct effect on the adsorption capacities of the ASW surface. Small molecules can accrete or form at the surface, adsorbed on the dangling OH groups of surface water molecules. This behaviour allows further reactivity which, in turn, could lead to more complex molecular systems. We have already demonstrated that selective IR irradiations of surface water molecules induce a modification of the surface and the production of a new monomer species which bonds to the surface via its two electronic doublets. However, we did not probe the structure of the dangling bands, namely their homogeneity or inhomogeneity. The structure and orientation of these surface molecules are closely linked to the way the surface can relax its vibrational energy. In this work, we have focussed our attention on the two dH dangling bonds, carrying out a series of selective irradiations which reveal the inhomogeneity of these surface modes. We have also studied the effects of irradiation duration on the surface reorientation, determining that the maximum photoinduced isomerisation yield is ∼15%.

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“…: Table of Contents graphic ASW is a molecular system which has long provoked interest due, in part, to its role in the formation of molecules key to the origins of life [1,2,3,4,5]. ASW has long been known to accrete small molecules such as CO, H 2 O, N 2 , or CH 4 [2,6,7], initiating chemical and photochemical surface reactivity [2,8,9].…”

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confidence: 99%

Unveiling the Surface Structure of Amorphous Solid Water via Selective Infrared Irradiation of OH Stretching Modes

Noble

Martin

Fraser

et al. 2014

J. Phys. Chem. Lett.

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In the quest to understand the formation of the building blocks of life, amorphous solid water (ASW) is one of the most widely studied molecular systems. Indeed, ASW is ubiquitous in the cold interstellar medium (ISM), where ASW-coated dust grains provide a catalytic surface for solid phase chemistry, and is believed to be present in the Earth's atmosphere at high altitudes. It has been shown that the ice surface adsorbs small molecules such as CO, N 2 , or CH 4 , most likely at OH groups dangling from the surface. Our study presents completely new insights concerning the behaviour of ASW upon selective infrared (IR) irradiation of its dangling modes. When irradiated, these surface H 2 O molecules reorganise, predominantly forming a stabilised monomer-like water mode on the ice surface. We show that we systematically provoke "hole-burning" effects (or net loss of oscillators) at the wavelength of irradiation and reproduce the same absorbed water monomer on the ASW surface. Our study suggests that all dangling modes share one common channel of vibrational relaxation; the ice remains amorphous but with a reduced range of binding sites, and thus an altered catalytic capacity.

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Quantum study of the adsorption of small molecules on ice: The infrared frequency of the surface hydroxyl group and the vibrational stark effect

Cited by 33 publications

References 55 publications

Using laboratory studies of CO-H₂O ices to understand the non-detection of a 2152 cm⁻¹(4.647 μm) band in the spectra of interstellar ices

Using laboratory studies of CO-H₂O ices to understand the non-detection of a 2152 cm⁻¹(4.647 μm) band in the spectra of interstellar ices

Inhomogeneity of the amorphous solid water dangling bonds

Unveiling the Surface Structure of Amorphous Solid Water via Selective Infrared Irradiation of OH Stretching Modes

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Quantum study of the adsorption of small molecules on ice: The infrared frequency of the surface hydroxyl group and the vibrational stark effect

Cited by 33 publications

References 55 publications

Using laboratory studies of CO-H2O ices to understand the non-detection of a 2152 cm−1(4.647 μm) band in the spectra of interstellar ices

Using laboratory studies of CO-H2O ices to understand the non-detection of a 2152 cm−1(4.647 μm) band in the spectra of interstellar ices

Inhomogeneity of the amorphous solid water dangling bonds

Unveiling the Surface Structure of Amorphous Solid Water via Selective Infrared Irradiation of OH Stretching Modes

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Using laboratory studies of CO-H₂O ices to understand the non-detection of a 2152 cm⁻¹(4.647 μm) band in the spectra of interstellar ices

Using laboratory studies of CO-H₂O ices to understand the non-detection of a 2152 cm⁻¹(4.647 μm) band in the spectra of interstellar ices