The interstellar gas-phase formation of CO2 - Assisted or not by water molecules?

Using state of the art methods of quantum chemistry, potential energy surfaces for the formation of CO2 (superscript 1 sigma superscript + subscript g)and CO2 (superscript 3 B subscript 2) from CO + O (superscript 1 D) and CO + O (superscript 3 P), respectively, have been studied. At the MRSDCI leve...

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Main Authors: Rohl, Andrew, Talbi, D., Chandler, G.
Format: Journal Article
Published: Elsevier B.V 2006
Subjects:
Online Access:http://hdl.handle.net/20.500.11937/32293
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author Rohl, Andrew
Talbi, D.
Chandler, G.
author_facet Rohl, Andrew
Talbi, D.
Chandler, G.
author_sort Rohl, Andrew
building Curtin Institutional Repository
collection Online Access
description Using state of the art methods of quantum chemistry, potential energy surfaces for the formation of CO2 (superscript 1 sigma superscript + subscript g)and CO2 (superscript 3 B subscript 2) from CO + O (superscript 1 D) and CO + O (superscript 3 P), respectively, have been studied. At the MRSDCI level, we show that the formation of CO2 (superscript 1 sigma superscript + subscript g) from O (superscript 3 P) is strongly connected with the height of the barrier localized on the CO + O (superscript 3 P) entrance channel. At the CCSD(T) level with a large basis set we calculate this barrier to be 5.9 kcal/mol. Consequently, we confirm that the gas-phase formation of CO2 in interstellar molecular clouds is inefficient. To mimic the formation of CO2, through the Eley-Rideal mechanism, on the water ice surfaces of interstellar grains, we have extended our study to consider the formation of CO2 in the presence of water molecules. We show, using density functional and CCSD(T) methods, that the barrier located on the CO + O (superscript 3 P) reaction entrance channel is hardly affected by the presence of water molecules. We therefore suggest that CO2 formation, through the Eley-Rideal mechanism, on the water ice surfaces of interstellar grains, should be inefficient too.
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spelling curtin-20.500.11937-322932017-09-13T15:55:37Z The interstellar gas-phase formation of CO2 - Assisted or not by water molecules? Rohl, Andrew Talbi, D. Chandler, G. Interstellar chemistry DFT methods Ab initio calculations CO2 formation Using state of the art methods of quantum chemistry, potential energy surfaces for the formation of CO2 (superscript 1 sigma superscript + subscript g)and CO2 (superscript 3 B subscript 2) from CO + O (superscript 1 D) and CO + O (superscript 3 P), respectively, have been studied. At the MRSDCI level, we show that the formation of CO2 (superscript 1 sigma superscript + subscript g) from O (superscript 3 P) is strongly connected with the height of the barrier localized on the CO + O (superscript 3 P) entrance channel. At the CCSD(T) level with a large basis set we calculate this barrier to be 5.9 kcal/mol. Consequently, we confirm that the gas-phase formation of CO2 in interstellar molecular clouds is inefficient. To mimic the formation of CO2, through the Eley-Rideal mechanism, on the water ice surfaces of interstellar grains, we have extended our study to consider the formation of CO2 in the presence of water molecules. We show, using density functional and CCSD(T) methods, that the barrier located on the CO + O (superscript 3 P) reaction entrance channel is hardly affected by the presence of water molecules. We therefore suggest that CO2 formation, through the Eley-Rideal mechanism, on the water ice surfaces of interstellar grains, should be inefficient too. 2006 Journal Article http://hdl.handle.net/20.500.11937/32293 10.1016/j.chemphys.2005.07.033 Elsevier B.V restricted
spellingShingle Interstellar chemistry
DFT methods
Ab initio calculations
CO2 formation
Rohl, Andrew
Talbi, D.
Chandler, G.
The interstellar gas-phase formation of CO2 - Assisted or not by water molecules?
title The interstellar gas-phase formation of CO2 - Assisted or not by water molecules?
title_full The interstellar gas-phase formation of CO2 - Assisted or not by water molecules?
title_fullStr The interstellar gas-phase formation of CO2 - Assisted or not by water molecules?
title_full_unstemmed The interstellar gas-phase formation of CO2 - Assisted or not by water molecules?
title_short The interstellar gas-phase formation of CO2 - Assisted or not by water molecules?
title_sort interstellar gas-phase formation of co2 - assisted or not by water molecules?
topic Interstellar chemistry
DFT methods
Ab initio calculations
CO2 formation
url http://hdl.handle.net/20.500.11937/32293