Quantum chemical study of the structure, spectroscopy and reactivity of NO+.(H2O)n=1-5 clusters

Quantum chemical methods including Møller-Plesset perturbation (MP2) theory and density functional theory (DFT) have been used to study the structure, spectroscopy and reactivity of NO+.(H2O)n=1−5 clusters. MP2/6-311++G** calculations are shown to describe the structure and spectroscopy of the clust...

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Main Authors:	Linton, Kirsty A., Wright, Timothy G., Besley, Nicholas A.
Format:	Article
Language:	English
Published:	Royal Society of Chemistry 2017
Online Access:	http://eprints.nottingham.ac.uk/46528/ http://eprints.nottingham.ac.uk/46528/1/Nick%20Besley%20Quantum%20Chemical%20Study.pdf

id	nottingham-46528
recordtype	eprints
spelling	nottingham-465282018-06-26T12:42:04Z http://eprints.nottingham.ac.uk/46528/ Quantum chemical study of the structure, spectroscopy and reactivity of NO+.(H2O)n=1-5 clusters Linton, Kirsty A. Wright, Timothy G. Besley, Nicholas A. Quantum chemical methods including Møller-Plesset perturbation (MP2) theory and density functional theory (DFT) have been used to study the structure, spectroscopy and reactivity of NO+.(H2O)n=1−5 clusters. MP2/6-311++G** calculations are shown to describe the structure and spectroscopy of the clusters well. DFT calculations with exchange-correlation functionals with a low fraction of Hartree-Fock exchange give a binding energy of NO+.(H2O) that is too high and incorrectly predict the lowest energy structure of NO+.(H2O)2, and this error may be associated with a delocalisation of charge onto the water molecule directly binding to NO+. Ab initio molecular dynamics (AIMD) simulations were performed to study the NO+.(H2O)5 → H+.(H2O)4 + HONO reaction to investigate the formation of HONO from NO+.(H2O)5. Whether an intracluster reaction to form HONO is observed depends on the level of electronic structure theory used. Of note is that methods that accurately describe the relative energies of the product and reactant clusters did not show reactions on the time-scales studied. This suggests that in the upper atmosphere the reaction may occur owing to the energy present in the NO+.(H2O)5 complex following its formation. Royal Society of Chemistry 2017-09-11 Article PeerReviewed application/pdf en http://eprints.nottingham.ac.uk/46528/1/Nick%20Besley%20Quantum%20Chemical%20Study.pdf Linton, Kirsty A. and Wright, Timothy G. and Besley, Nicholas A. (2017) Quantum chemical study of the structure, spectroscopy and reactivity of NO+.(H2O)n=1-5 clusters. Philosophical Transactions A: Mathematical, Physical and Engineering Sciences . ISSN 1471-2962 (In Press)
repository_type	Digital Repository
institution_category	Local University
institution	University of Nottingham Malaysia Campus
building	Nottingham Research Data Repository
collection	Online Access
language	English
description	Quantum chemical methods including Møller-Plesset perturbation (MP2) theory and density functional theory (DFT) have been used to study the structure, spectroscopy and reactivity of NO+.(H2O)n=1−5 clusters. MP2/6-311++G** calculations are shown to describe the structure and spectroscopy of the clusters well. DFT calculations with exchange-correlation functionals with a low fraction of Hartree-Fock exchange give a binding energy of NO+.(H2O) that is too high and incorrectly predict the lowest energy structure of NO+.(H2O)2, and this error may be associated with a delocalisation of charge onto the water molecule directly binding to NO+. Ab initio molecular dynamics (AIMD) simulations were performed to study the NO+.(H2O)5 → H+.(H2O)4 + HONO reaction to investigate the formation of HONO from NO+.(H2O)5. Whether an intracluster reaction to form HONO is observed depends on the level of electronic structure theory used. Of note is that methods that accurately describe the relative energies of the product and reactant clusters did not show reactions on the time-scales studied. This suggests that in the upper atmosphere the reaction may occur owing to the energy present in the NO+.(H2O)5 complex following its formation.
format	Article
author	Linton, Kirsty A. Wright, Timothy G. Besley, Nicholas A.
spellingShingle	Linton, Kirsty A. Wright, Timothy G. Besley, Nicholas A. Quantum chemical study of the structure, spectroscopy and reactivity of NO+.(H2O)n=1-5 clusters
author_facet	Linton, Kirsty A. Wright, Timothy G. Besley, Nicholas A.
author_sort	Linton, Kirsty A.
title	Quantum chemical study of the structure, spectroscopy and reactivity of NO+.(H2O)n=1-5 clusters
title_short	Quantum chemical study of the structure, spectroscopy and reactivity of NO+.(H2O)n=1-5 clusters
title_full	Quantum chemical study of the structure, spectroscopy and reactivity of NO+.(H2O)n=1-5 clusters
title_fullStr	Quantum chemical study of the structure, spectroscopy and reactivity of NO+.(H2O)n=1-5 clusters
title_full_unstemmed	Quantum chemical study of the structure, spectroscopy and reactivity of NO+.(H2O)n=1-5 clusters
title_sort	quantum chemical study of the structure, spectroscopy and reactivity of no+.(h2o)n=1-5 clusters
publisher	Royal Society of Chemistry
publishDate	2017
url	http://eprints.nottingham.ac.uk/46528/ http://eprints.nottingham.ac.uk/46528/1/Nick%20Besley%20Quantum%20Chemical%20Study.pdf
first_indexed	2018-09-06T13:47:21Z
last_indexed	2018-09-06T13:47:21Z
_version_	1610866115991306240

Quantum chemical study of the structure, spectroscopy and reactivity of NO+.(H2O)n=1-5 clusters

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