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Conference Paper: Determination of crbon dioxide cluster structures and binding energies from quantum chemistry: magic number and temperature effects in (CO2)n with 2<= n<=16
Title | Determination of crbon dioxide cluster structures and binding energies from quantum chemistry: magic number and temperature effects in (CO2)n with 2<= n<=16 |
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Authors | |
Keywords | 3612 Reactions and phase equilibria 3621 Mantle processes 3630 Experimental mineralogy and petrology 8430 Volcanic gases |
Issue Date | 2014 |
Publisher | American Geophysical Union,. |
Citation | The 47th Annual Fall Meeting of the American Geophysical Union (AGU 2014), San Francisco, CA., 15-19 December 2014. How to Cite? |
Abstract | Weak intermolecular interactions play an important role in nature and are involved in the stabilization of a variety of different molecular aggregates. Carbon dioxide clusters (CO2)n are a good example in which monomers interact through London dispersion forces. The ability to accurately describe these types of interactions is crucial in understanding fundamental molecular-scale processes controlling the chemistry of carbon dioxide, ranging from CO2 self-organization into monolayer films on metal and mineral surfaces, formation of CO2 clouds and molecular interactions in supercritical CO2. Weak interactions in (CO2)n clusters pose a challenge for experimental techniques, and are therefore in many cases either difficult or impossible to explore. Density functional theory with dispersion correction (DFT-D), on the other hand, can provide insight into intermolecular interactions among CO2 molecules, provided that dispersion correction is properly accounted for. In this presentation results from dispersion sensitive DFT (M05-2X, B97-D, B2PLYPD) and MP2 theory will be shown, that describe interactions in (CO2)n clusters over a broad range of temperatures, and in particular, in those clusters with magic number sizes 6 and 13. Briefly, structure determinations and thermodynamic calculations for (CO2)n clustering reactions by DFT-D compare well against benchmark MP2 and CCSD(T)/CBS results, and therefore may be extended to significantly larger systems than accessible with highly correlated methods. The stepwise free energies of CO2 cluster formation at temperatures from 60-400K reveal valuable new insights, the most important being that the stacked cyclic hexamer and tridecameric cluster, consisting of a 3-6-3 ring structure with a centrally enclosed CO2 monomer, are highly stable clusters and therefore should be spectroscopically detectable. These results indicate that DFT-D provides an accurate and cost effective description of non-covalent interactions in (CO2) clusters, and thus may provide important information on nucleation phenomena in CO2 phases with gas-like densities. |
Description | Meeting Theme: Urban Areas as Seen from Space Abstract no. V13A-4760 |
Persistent Identifier | http://hdl.handle.net/10722/233294 |
DC Field | Value | Language |
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dc.contributor.author | Lemke, KH | - |
dc.date.accessioned | 2016-09-20T05:35:54Z | - |
dc.date.available | 2016-09-20T05:35:54Z | - |
dc.date.issued | 2014 | - |
dc.identifier.citation | The 47th Annual Fall Meeting of the American Geophysical Union (AGU 2014), San Francisco, CA., 15-19 December 2014. | - |
dc.identifier.uri | http://hdl.handle.net/10722/233294 | - |
dc.description | Meeting Theme: Urban Areas as Seen from Space | - |
dc.description | Abstract no. V13A-4760 | - |
dc.description.abstract | Weak intermolecular interactions play an important role in nature and are involved in the stabilization of a variety of different molecular aggregates. Carbon dioxide clusters (CO2)n are a good example in which monomers interact through London dispersion forces. The ability to accurately describe these types of interactions is crucial in understanding fundamental molecular-scale processes controlling the chemistry of carbon dioxide, ranging from CO2 self-organization into monolayer films on metal and mineral surfaces, formation of CO2 clouds and molecular interactions in supercritical CO2. Weak interactions in (CO2)n clusters pose a challenge for experimental techniques, and are therefore in many cases either difficult or impossible to explore. Density functional theory with dispersion correction (DFT-D), on the other hand, can provide insight into intermolecular interactions among CO2 molecules, provided that dispersion correction is properly accounted for. In this presentation results from dispersion sensitive DFT (M05-2X, B97-D, B2PLYPD) and MP2 theory will be shown, that describe interactions in (CO2)n clusters over a broad range of temperatures, and in particular, in those clusters with magic number sizes 6 and 13. Briefly, structure determinations and thermodynamic calculations for (CO2)n clustering reactions by DFT-D compare well against benchmark MP2 and CCSD(T)/CBS results, and therefore may be extended to significantly larger systems than accessible with highly correlated methods. The stepwise free energies of CO2 cluster formation at temperatures from 60-400K reveal valuable new insights, the most important being that the stacked cyclic hexamer and tridecameric cluster, consisting of a 3-6-3 ring structure with a centrally enclosed CO2 monomer, are highly stable clusters and therefore should be spectroscopically detectable. These results indicate that DFT-D provides an accurate and cost effective description of non-covalent interactions in (CO2) clusters, and thus may provide important information on nucleation phenomena in CO2 phases with gas-like densities. | - |
dc.language | eng | - |
dc.publisher | American Geophysical Union,. | - |
dc.relation.ispartof | Fall Meeting of the American Geophysical Union, AGU 2014 | - |
dc.subject | 3612 Reactions and phase equilibria | - |
dc.subject | 3621 Mantle processes | - |
dc.subject | 3630 Experimental mineralogy and petrology | - |
dc.subject | 8430 Volcanic gases | - |
dc.title | Determination of crbon dioxide cluster structures and binding energies from quantum chemistry: magic number and temperature effects in (CO2)n with 2<= n<=16 | - |
dc.type | Conference_Paper | - |
dc.identifier.email | Lemke, KH: kono@hku.hk | - |
dc.identifier.authority | Lemke, KH=rp00729 | - |
dc.identifier.hkuros | 267098 | - |