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Issue 7, 2009
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Quantum chemical studies of the adsorption of single acetone molecules on hexagonal ice Ih and cubic ice Ic

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Abstract

The interaction energies of free acetone molecules with surfaces of two different ice polymorphs have been investigated by quantum chemical methods. Special emphasis has been given to sites for adsorption on the (0001) surface of hexagonal ice (Ih) and the ([1 with combining macron]01) surface of cubic ice (Ic), respectively. The structural optimisations made use of conventional electronic structure methods including HF and B3LYP using moderate basis sets up to 6-31+G(d) as well as local and ONIOM methods using 2 or 3 layers which were treated at different levels of theory. The adsorption energies at T = 0 K were calculated for the optimised adsorption geometries performing single points at the B3LYP, MP2 and LMP2 level in conjunction with valence triple-ζ basis sets up to 6-311+G(d,p). Including corrections for basis set superposition errors (BSSE) the most extensive calculations provide adsorption energies (T = 0 K) of −39.1 and −57.5 kJ mol−1 for the energetically most favourable sites for adsorption of a single acetone molecule on ice Ih and ice Ic, respectively. By vibrational analysis this can be transformed to adsorption enthalpies at around a temperature of 200 K yielding values of −31.5 for adsorption on ice Ih and −49.9 kJ mol−1 for adsorption on ice Ic. The current results support experimental observations of Behr et al. (J. Phys. Chem. A, 2006, 110, 8098) in which evidence was presented that acetone adsorbs on ice around 200 K at two different sites; each of which has a different adsorption enthalpy.

Graphical abstract: Quantum chemical studies of the adsorption of single acetone molecules on hexagonal ice Ih and cubic ice Ic

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Publication details

The article was received on 19 Aug 2008, accepted on 30 Oct 2008 and first published on 17 Dec 2008


Article type: Paper
DOI: 10.1039/B814467B
Citation: Phys. Chem. Chem. Phys., 2009,11, 1033-1042
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    Quantum chemical studies of the adsorption of single acetone molecules on hexagonal ice Ih and cubic ice Ic

    H. Somnitz, Phys. Chem. Chem. Phys., 2009, 11, 1033
    DOI: 10.1039/B814467B

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