Quasiclassical Trajectory Simulations of OH(v) + NO2 → HONO2 → OH(v‘) + NO2:  Capture and Vibrational Deactivation Rate Constants

Quasiclassical trajectory calculations are used to investigate the dynamics of the OH(v) + NO2 → HONO2* → OH(v‘) + NO2 recombination/dissociation reaction on an analytic potential energy surface (PES) that gives good agreement with the known structure and vibrational frequencies of nitric acid. The...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2006-02, Vol.110 (4), p.1267-1277
Hauptverfasser: Liu, Yong, Lohr, Lawrence L, Barker, John R
Format: Artikel
Sprache:eng
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page 1277
container_issue 4
container_start_page 1267
container_title The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory
container_volume 110
creator Liu, Yong
Lohr, Lawrence L
Barker, John R
description Quasiclassical trajectory calculations are used to investigate the dynamics of the OH(v) + NO2 → HONO2* → OH(v‘) + NO2 recombination/dissociation reaction on an analytic potential energy surface (PES) that gives good agreement with the known structure and vibrational frequencies of nitric acid. The calculated recombination rate constants depend only weakly on temperature and on the initial vibrational energy level of OH(v). The magnitude of the recombination rate constant is sensitive to the potential function describing the newly formed bond and to the switching functions in the PES that attenuate inter-mode interactions at long range. The lifetime of the nascent excited HONO2* depends strongly not only on its internal energy but also on the identity of the initial state, in disagreement with statistical theory. This disagreement is probably due to the effects of slow intramolecular vibrational energy redistribution (IVR) from the initially excited OH stretching mode. The vibrational energy distribution of product OH(v‘) radicals is different from statistical distributions, a result consistent with the effects of slow IVR. Nonetheless, the trajectory results predict that vibrational deactivation of OH(v) via the HONO2* transient complex is ∼90% efficient, almost independent of initial OH(v) vibrational level, in qualitative agreement with recent experiments. Tests are also carried out using the HONO2 PES, but assuming the weaker O−O bond strength found in HOONO (peroxynitrous acid). In this case, the predicted vibrational deactivation efficiencies are significantly lower and depend strongly on the initial vibrational state of OH(v), in disagreement with experiments. This disagreement suggests that the actual HOONO PES may contain more inter-mode coupling than found in the present model PES, which is based on HONO2. For nitric acid, the measured vibrational deactivation rate constant is a useful proxy for the recombination rate, but IVR randomization of energy is not complete, suggesting that the efficacy of the proxy method must be evaluated on a case-by-case basis.
doi_str_mv 10.1021/jp053099a
format Article
fullrecord <record><control><sourceid>proquest_pubme</sourceid><recordid>TN_cdi_proquest_miscellaneous_70736356</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>70736356</sourcerecordid><originalsourceid>FETCH-LOGICAL-a273t-c27231a982a025665d604765dc9ad0273a12cdcd83c2112124d8ae3537903353</originalsourceid><addsrcrecordid>eNo9kTtPwzAUhS0E4lEY-APICwiEAn7UccIG4VEkRAutWK2LY6SUtCm2U9GtExIrE7-vvwTTFpZ77tX5dIZzEdql5IQSRk_7IyI4SVNYQZtUMBIJRsVq2EmSRiLm6Qbacq5PCKGcNdfRBo2bXMhEbqLPhxpcoUtwYUKJexb6RvvKTnC3GNQl-KIaOly94HbrcHyEj_F9m-HZxxdutf-2X2c2_V6aZ7PpJ85g5GtrMAxz_FQ823lMiL80oH0xnp_4EbzBWYj3MPRuG629QOnMzlIbqHd91cta0V375jY7v4uASe4jzSTjFNKEAWEijkUek6YMolPISUCAMp3rPOGaUcooa-YJGC64TAkP0kAHi9iRrd5q47waFE6bsoShqWqnJJE85qG0BtpbgvXzwORqZIsB2In66y4A0QIonDfv_z7YVxVLLoXqdbqqc80vbrpppi4Dv7_gQTvVr2obCnGKEvX7Q_X_Q_4DWmGLGQ</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>70736356</pqid></control><display><type>article</type><title>Quasiclassical Trajectory Simulations of OH(v) + NO2 → HONO2 → OH(v‘) + NO2:  Capture and Vibrational Deactivation Rate Constants</title><source>American Chemical Society</source><creator>Liu, Yong ; Lohr, Lawrence L ; Barker, John R</creator><creatorcontrib>Liu, Yong ; Lohr, Lawrence L ; Barker, John R</creatorcontrib><description>Quasiclassical trajectory calculations are used to investigate the dynamics of the OH(v) + NO2 → HONO2* → OH(v‘) + NO2 recombination/dissociation reaction on an analytic potential energy surface (PES) that gives good agreement with the known structure and vibrational frequencies of nitric acid. The calculated recombination rate constants depend only weakly on temperature and on the initial vibrational energy level of OH(v). The magnitude of the recombination rate constant is sensitive to the potential function describing the newly formed bond and to the switching functions in the PES that attenuate inter-mode interactions at long range. The lifetime of the nascent excited HONO2* depends strongly not only on its internal energy but also on the identity of the initial state, in disagreement with statistical theory. This disagreement is probably due to the effects of slow intramolecular vibrational energy redistribution (IVR) from the initially excited OH stretching mode. The vibrational energy distribution of product OH(v‘) radicals is different from statistical distributions, a result consistent with the effects of slow IVR. Nonetheless, the trajectory results predict that vibrational deactivation of OH(v) via the HONO2* transient complex is ∼90% efficient, almost independent of initial OH(v) vibrational level, in qualitative agreement with recent experiments. Tests are also carried out using the HONO2 PES, but assuming the weaker O−O bond strength found in HOONO (peroxynitrous acid). In this case, the predicted vibrational deactivation efficiencies are significantly lower and depend strongly on the initial vibrational state of OH(v), in disagreement with experiments. This disagreement suggests that the actual HOONO PES may contain more inter-mode coupling than found in the present model PES, which is based on HONO2. For nitric acid, the measured vibrational deactivation rate constant is a useful proxy for the recombination rate, but IVR randomization of energy is not complete, suggesting that the efficacy of the proxy method must be evaluated on a case-by-case basis.</description><identifier>ISSN: 1089-5639</identifier><identifier>EISSN: 1520-5215</identifier><identifier>DOI: 10.1021/jp053099a</identifier><identifier>PMID: 16435787</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><ispartof>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, &amp; general theory, 2006-02, Vol.110 (4), p.1267-1277</ispartof><rights>Copyright © 2006 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jp053099a$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jp053099a$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/16435787$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Liu, Yong</creatorcontrib><creatorcontrib>Lohr, Lawrence L</creatorcontrib><creatorcontrib>Barker, John R</creatorcontrib><title>Quasiclassical Trajectory Simulations of OH(v) + NO2 → HONO2 → OH(v‘) + NO2:  Capture and Vibrational Deactivation Rate Constants</title><title>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, &amp; general theory</title><addtitle>J. Phys. Chem. A</addtitle><description>Quasiclassical trajectory calculations are used to investigate the dynamics of the OH(v) + NO2 → HONO2* → OH(v‘) + NO2 recombination/dissociation reaction on an analytic potential energy surface (PES) that gives good agreement with the known structure and vibrational frequencies of nitric acid. The calculated recombination rate constants depend only weakly on temperature and on the initial vibrational energy level of OH(v). The magnitude of the recombination rate constant is sensitive to the potential function describing the newly formed bond and to the switching functions in the PES that attenuate inter-mode interactions at long range. The lifetime of the nascent excited HONO2* depends strongly not only on its internal energy but also on the identity of the initial state, in disagreement with statistical theory. This disagreement is probably due to the effects of slow intramolecular vibrational energy redistribution (IVR) from the initially excited OH stretching mode. The vibrational energy distribution of product OH(v‘) radicals is different from statistical distributions, a result consistent with the effects of slow IVR. Nonetheless, the trajectory results predict that vibrational deactivation of OH(v) via the HONO2* transient complex is ∼90% efficient, almost independent of initial OH(v) vibrational level, in qualitative agreement with recent experiments. Tests are also carried out using the HONO2 PES, but assuming the weaker O−O bond strength found in HOONO (peroxynitrous acid). In this case, the predicted vibrational deactivation efficiencies are significantly lower and depend strongly on the initial vibrational state of OH(v), in disagreement with experiments. This disagreement suggests that the actual HOONO PES may contain more inter-mode coupling than found in the present model PES, which is based on HONO2. For nitric acid, the measured vibrational deactivation rate constant is a useful proxy for the recombination rate, but IVR randomization of energy is not complete, suggesting that the efficacy of the proxy method must be evaluated on a case-by-case basis.</description><issn>1089-5639</issn><issn>1520-5215</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2006</creationdate><recordtype>article</recordtype><recordid>eNo9kTtPwzAUhS0E4lEY-APICwiEAn7UccIG4VEkRAutWK2LY6SUtCm2U9GtExIrE7-vvwTTFpZ77tX5dIZzEdql5IQSRk_7IyI4SVNYQZtUMBIJRsVq2EmSRiLm6Qbacq5PCKGcNdfRBo2bXMhEbqLPhxpcoUtwYUKJexb6RvvKTnC3GNQl-KIaOly94HbrcHyEj_F9m-HZxxdutf-2X2c2_V6aZ7PpJ85g5GtrMAxz_FQ823lMiL80oH0xnp_4EbzBWYj3MPRuG629QOnMzlIbqHd91cta0V375jY7v4uASe4jzSTjFNKEAWEijkUek6YMolPISUCAMp3rPOGaUcooa-YJGC64TAkP0kAHi9iRrd5q47waFE6bsoShqWqnJJE85qG0BtpbgvXzwORqZIsB2In66y4A0QIonDfv_z7YVxVLLoXqdbqqc80vbrpppi4Dv7_gQTvVr2obCnGKEvX7Q_X_Q_4DWmGLGQ</recordid><startdate>20060202</startdate><enddate>20060202</enddate><creator>Liu, Yong</creator><creator>Lohr, Lawrence L</creator><creator>Barker, John R</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>NPM</scope><scope>7X8</scope></search><sort><creationdate>20060202</creationdate><title>Quasiclassical Trajectory Simulations of OH(v) + NO2 → HONO2 → OH(v‘) + NO2:  Capture and Vibrational Deactivation Rate Constants</title><author>Liu, Yong ; Lohr, Lawrence L ; Barker, John R</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a273t-c27231a982a025665d604765dc9ad0273a12cdcd83c2112124d8ae3537903353</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2006</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Liu, Yong</creatorcontrib><creatorcontrib>Lohr, Lawrence L</creatorcontrib><creatorcontrib>Barker, John R</creatorcontrib><collection>Istex</collection><collection>PubMed</collection><collection>MEDLINE - Academic</collection><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, &amp; general theory</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Liu, Yong</au><au>Lohr, Lawrence L</au><au>Barker, John R</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Quasiclassical Trajectory Simulations of OH(v) + NO2 → HONO2 → OH(v‘) + NO2:  Capture and Vibrational Deactivation Rate Constants</atitle><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, &amp; general theory</jtitle><addtitle>J. Phys. Chem. A</addtitle><date>2006-02-02</date><risdate>2006</risdate><volume>110</volume><issue>4</issue><spage>1267</spage><epage>1277</epage><pages>1267-1277</pages><issn>1089-5639</issn><eissn>1520-5215</eissn><abstract>Quasiclassical trajectory calculations are used to investigate the dynamics of the OH(v) + NO2 → HONO2* → OH(v‘) + NO2 recombination/dissociation reaction on an analytic potential energy surface (PES) that gives good agreement with the known structure and vibrational frequencies of nitric acid. The calculated recombination rate constants depend only weakly on temperature and on the initial vibrational energy level of OH(v). The magnitude of the recombination rate constant is sensitive to the potential function describing the newly formed bond and to the switching functions in the PES that attenuate inter-mode interactions at long range. The lifetime of the nascent excited HONO2* depends strongly not only on its internal energy but also on the identity of the initial state, in disagreement with statistical theory. This disagreement is probably due to the effects of slow intramolecular vibrational energy redistribution (IVR) from the initially excited OH stretching mode. The vibrational energy distribution of product OH(v‘) radicals is different from statistical distributions, a result consistent with the effects of slow IVR. Nonetheless, the trajectory results predict that vibrational deactivation of OH(v) via the HONO2* transient complex is ∼90% efficient, almost independent of initial OH(v) vibrational level, in qualitative agreement with recent experiments. Tests are also carried out using the HONO2 PES, but assuming the weaker O−O bond strength found in HOONO (peroxynitrous acid). In this case, the predicted vibrational deactivation efficiencies are significantly lower and depend strongly on the initial vibrational state of OH(v), in disagreement with experiments. This disagreement suggests that the actual HOONO PES may contain more inter-mode coupling than found in the present model PES, which is based on HONO2. For nitric acid, the measured vibrational deactivation rate constant is a useful proxy for the recombination rate, but IVR randomization of energy is not complete, suggesting that the efficacy of the proxy method must be evaluated on a case-by-case basis.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>16435787</pmid><doi>10.1021/jp053099a</doi><tpages>11</tpages></addata></record>
fulltext fulltext
identifier ISSN: 1089-5639
ispartof The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 2006-02, Vol.110 (4), p.1267-1277
issn 1089-5639
1520-5215
language eng
recordid cdi_proquest_miscellaneous_70736356
source American Chemical Society
title Quasiclassical Trajectory Simulations of OH(v) + NO2 → HONO2 → OH(v‘) + NO2:  Capture and Vibrational Deactivation Rate Constants
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-25T06%3A15%3A12IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_pubme&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Quasiclassical%20Trajectory%20Simulations%20of%20OH(v)%20+%20NO2%20%E2%86%92%20HONO2%20%E2%86%92%20OH(v%E2%80%98)%20+%20NO2:%E2%80%89%20Capture%20and%20Vibrational%20Deactivation%20Rate%20Constants&rft.jtitle=The%20journal%20of%20physical%20chemistry.%20A,%20Molecules,%20spectroscopy,%20kinetics,%20environment,%20&%20general%20theory&rft.au=Liu,%20Yong&rft.date=2006-02-02&rft.volume=110&rft.issue=4&rft.spage=1267&rft.epage=1277&rft.pages=1267-1277&rft.issn=1089-5639&rft.eissn=1520-5215&rft_id=info:doi/10.1021/jp053099a&rft_dat=%3Cproquest_pubme%3E70736356%3C/proquest_pubme%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=70736356&rft_id=info:pmid/16435787&rfr_iscdi=true