The branching ratio between reaction and relaxation in the removal of H2O from its |04〉− vibrational state in collisions with H atoms

The removal of H2O molecules from their |04〉− vibrational state in collisions with H atoms can occur both by reaction, producing OH(v=0)+H2, and by nonreactive relaxation. We report an experimental measurement of the fraction (freac) that occurs by reaction. The value of freac is determined by compa...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:The Journal of chemical physics 2001-09, Vol.115 (10), p.4586-4592
Hauptverfasser: Barnes, Peter W., Sims, Ian R., Smith, Ian W. M., Lendvay, György, Schatz, George C.
Format: Artikel
Sprache:eng
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page 4592
container_issue 10
container_start_page 4586
container_title The Journal of chemical physics
container_volume 115
creator Barnes, Peter W.
Sims, Ian R.
Smith, Ian W. M.
Lendvay, György
Schatz, George C.
description The removal of H2O molecules from their |04〉− vibrational state in collisions with H atoms can occur both by reaction, producing OH(v=0)+H2, and by nonreactive relaxation. We report an experimental measurement of the fraction (freac) that occurs by reaction. The value of freac is determined by comparing the yields of OH from three experiments in which the same concentration of H2O(|04〉−) is prepared by overtone absorption of pulsed laser radiation and OH(v=0) is produced: (i) solely by the H+H2O(|04〉−) reaction; (ii) solely by the photodissociation of H2O(|04〉−) at 266 nm; and (iii) both by the photodissociation of H2O(|04〉−) and by the subsequent reaction of a fraction of the remaining H2O(|04〉−) with H atoms. Analysis of these experiments shows that freac=(0.34±0.11). The experimental results are compared with the results of two kinds of scattering calculations performed on a potential energy surface developed recently, specifically with this problem in mind. Using the vibrational coupled-channel infinite-order-sudden (VCC-IOS) method, rate coefficients have been calculated for individual vibrationally inelastic processes and then summed to find the rate coefficient (krelaxH) for total nonreactive relaxation from the |04〉− state. The quasiclassical trajectory (QCT) method has been used to calculate the rate coefficient (kreac) for reaction between H atoms and H2O(|04〉−). Both the calculated rate coefficient (i.e., krelaxH+kreac) for total loss from H2O(|04〉−) and the calculated branching ratio, freac=kreac/(krelaxH+kreac)=0.38, are in quite good agreement with the experimental values.
doi_str_mv 10.1063/1.1389304
format Article
fullrecord <record><control><sourceid>crossref</sourceid><recordid>TN_cdi_crossref_primary_10_1063_1_1389304</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>10_1063_1_1389304</sourcerecordid><originalsourceid>FETCH-LOGICAL-c142t-29b51b76da2eade3afc43c0a77ee116f81e459b97ff607bb7a6ec997c4005e3a3</originalsourceid><addsrcrecordid>eNotkL1OAzEQhC0EEiFQ8AZuKS6s7y52XKIICFKkNKE-rZ01MbofZFsJSBSUpOUR4UW4QKrRN5qZYhi7FDASIItrMRLFRBdQHrGBgInOlNRwzAYAuci0BHnKzmJ8BgCh8nLAdss1cROwtWvfPvGAyXfcUNoStTwQ2p5bju2qhxpf8Q99y1NfC9R0G6x55_gsX3AXuob7FPk7lD8fu-_PL77x5m-x7VMxYaJ91XZ17WNvRr71ac1nHFPXxHN24rCOdHHQIXu8u11OZ9l8cf8wvZlnVpR5ynJtxsIoucKccEUFOlsWFlApIiGkmwgqx9po5ZwEZYxCSVZrZUuAcR8vhuzqf9eGLsZArnoJvsHwVgmo9h9Wojp8WPwCNThniw</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>The branching ratio between reaction and relaxation in the removal of H2O from its |04〉− vibrational state in collisions with H atoms</title><source>American Institute of Physics (AIP) Journals</source><source>AIP Digital Archive</source><creator>Barnes, Peter W. ; Sims, Ian R. ; Smith, Ian W. M. ; Lendvay, György ; Schatz, George C.</creator><creatorcontrib>Barnes, Peter W. ; Sims, Ian R. ; Smith, Ian W. M. ; Lendvay, György ; Schatz, George C.</creatorcontrib><description>The removal of H2O molecules from their |04〉− vibrational state in collisions with H atoms can occur both by reaction, producing OH(v=0)+H2, and by nonreactive relaxation. We report an experimental measurement of the fraction (freac) that occurs by reaction. The value of freac is determined by comparing the yields of OH from three experiments in which the same concentration of H2O(|04〉−) is prepared by overtone absorption of pulsed laser radiation and OH(v=0) is produced: (i) solely by the H+H2O(|04〉−) reaction; (ii) solely by the photodissociation of H2O(|04〉−) at 266 nm; and (iii) both by the photodissociation of H2O(|04〉−) and by the subsequent reaction of a fraction of the remaining H2O(|04〉−) with H atoms. Analysis of these experiments shows that freac=(0.34±0.11). The experimental results are compared with the results of two kinds of scattering calculations performed on a potential energy surface developed recently, specifically with this problem in mind. Using the vibrational coupled-channel infinite-order-sudden (VCC-IOS) method, rate coefficients have been calculated for individual vibrationally inelastic processes and then summed to find the rate coefficient (krelaxH) for total nonreactive relaxation from the |04〉− state. The quasiclassical trajectory (QCT) method has been used to calculate the rate coefficient (kreac) for reaction between H atoms and H2O(|04〉−). Both the calculated rate coefficient (i.e., krelaxH+kreac) for total loss from H2O(|04〉−) and the calculated branching ratio, freac=kreac/(krelaxH+kreac)=0.38, are in quite good agreement with the experimental values.</description><identifier>ISSN: 0021-9606</identifier><identifier>EISSN: 1089-7690</identifier><identifier>DOI: 10.1063/1.1389304</identifier><language>eng</language><ispartof>The Journal of chemical physics, 2001-09, Vol.115 (10), p.4586-4592</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c142t-29b51b76da2eade3afc43c0a77ee116f81e459b97ff607bb7a6ec997c4005e3a3</citedby><cites>FETCH-LOGICAL-c142t-29b51b76da2eade3afc43c0a77ee116f81e459b97ff607bb7a6ec997c4005e3a3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,777,781,27905,27906</link.rule.ids></links><search><creatorcontrib>Barnes, Peter W.</creatorcontrib><creatorcontrib>Sims, Ian R.</creatorcontrib><creatorcontrib>Smith, Ian W. M.</creatorcontrib><creatorcontrib>Lendvay, György</creatorcontrib><creatorcontrib>Schatz, George C.</creatorcontrib><title>The branching ratio between reaction and relaxation in the removal of H2O from its |04〉− vibrational state in collisions with H atoms</title><title>The Journal of chemical physics</title><description>The removal of H2O molecules from their |04〉− vibrational state in collisions with H atoms can occur both by reaction, producing OH(v=0)+H2, and by nonreactive relaxation. We report an experimental measurement of the fraction (freac) that occurs by reaction. The value of freac is determined by comparing the yields of OH from three experiments in which the same concentration of H2O(|04〉−) is prepared by overtone absorption of pulsed laser radiation and OH(v=0) is produced: (i) solely by the H+H2O(|04〉−) reaction; (ii) solely by the photodissociation of H2O(|04〉−) at 266 nm; and (iii) both by the photodissociation of H2O(|04〉−) and by the subsequent reaction of a fraction of the remaining H2O(|04〉−) with H atoms. Analysis of these experiments shows that freac=(0.34±0.11). The experimental results are compared with the results of two kinds of scattering calculations performed on a potential energy surface developed recently, specifically with this problem in mind. Using the vibrational coupled-channel infinite-order-sudden (VCC-IOS) method, rate coefficients have been calculated for individual vibrationally inelastic processes and then summed to find the rate coefficient (krelaxH) for total nonreactive relaxation from the |04〉− state. The quasiclassical trajectory (QCT) method has been used to calculate the rate coefficient (kreac) for reaction between H atoms and H2O(|04〉−). Both the calculated rate coefficient (i.e., krelaxH+kreac) for total loss from H2O(|04〉−) and the calculated branching ratio, freac=kreac/(krelaxH+kreac)=0.38, are in quite good agreement with the experimental values.</description><issn>0021-9606</issn><issn>1089-7690</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2001</creationdate><recordtype>article</recordtype><recordid>eNotkL1OAzEQhC0EEiFQ8AZuKS6s7y52XKIICFKkNKE-rZ01MbofZFsJSBSUpOUR4UW4QKrRN5qZYhi7FDASIItrMRLFRBdQHrGBgInOlNRwzAYAuci0BHnKzmJ8BgCh8nLAdss1cROwtWvfPvGAyXfcUNoStTwQ2p5bju2qhxpf8Q99y1NfC9R0G6x55_gsX3AXuob7FPk7lD8fu-_PL77x5m-x7VMxYaJ91XZ17WNvRr71ac1nHFPXxHN24rCOdHHQIXu8u11OZ9l8cf8wvZlnVpR5ynJtxsIoucKccEUFOlsWFlApIiGkmwgqx9po5ZwEZYxCSVZrZUuAcR8vhuzqf9eGLsZArnoJvsHwVgmo9h9Wojp8WPwCNThniw</recordid><startdate>20010908</startdate><enddate>20010908</enddate><creator>Barnes, Peter W.</creator><creator>Sims, Ian R.</creator><creator>Smith, Ian W. M.</creator><creator>Lendvay, György</creator><creator>Schatz, George C.</creator><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20010908</creationdate><title>The branching ratio between reaction and relaxation in the removal of H2O from its |04〉− vibrational state in collisions with H atoms</title><author>Barnes, Peter W. ; Sims, Ian R. ; Smith, Ian W. M. ; Lendvay, György ; Schatz, George C.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c142t-29b51b76da2eade3afc43c0a77ee116f81e459b97ff607bb7a6ec997c4005e3a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2001</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Barnes, Peter W.</creatorcontrib><creatorcontrib>Sims, Ian R.</creatorcontrib><creatorcontrib>Smith, Ian W. M.</creatorcontrib><creatorcontrib>Lendvay, György</creatorcontrib><creatorcontrib>Schatz, George C.</creatorcontrib><collection>CrossRef</collection><jtitle>The Journal of chemical physics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Barnes, Peter W.</au><au>Sims, Ian R.</au><au>Smith, Ian W. M.</au><au>Lendvay, György</au><au>Schatz, George C.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>The branching ratio between reaction and relaxation in the removal of H2O from its |04〉− vibrational state in collisions with H atoms</atitle><jtitle>The Journal of chemical physics</jtitle><date>2001-09-08</date><risdate>2001</risdate><volume>115</volume><issue>10</issue><spage>4586</spage><epage>4592</epage><pages>4586-4592</pages><issn>0021-9606</issn><eissn>1089-7690</eissn><abstract>The removal of H2O molecules from their |04〉− vibrational state in collisions with H atoms can occur both by reaction, producing OH(v=0)+H2, and by nonreactive relaxation. We report an experimental measurement of the fraction (freac) that occurs by reaction. The value of freac is determined by comparing the yields of OH from three experiments in which the same concentration of H2O(|04〉−) is prepared by overtone absorption of pulsed laser radiation and OH(v=0) is produced: (i) solely by the H+H2O(|04〉−) reaction; (ii) solely by the photodissociation of H2O(|04〉−) at 266 nm; and (iii) both by the photodissociation of H2O(|04〉−) and by the subsequent reaction of a fraction of the remaining H2O(|04〉−) with H atoms. Analysis of these experiments shows that freac=(0.34±0.11). The experimental results are compared with the results of two kinds of scattering calculations performed on a potential energy surface developed recently, specifically with this problem in mind. Using the vibrational coupled-channel infinite-order-sudden (VCC-IOS) method, rate coefficients have been calculated for individual vibrationally inelastic processes and then summed to find the rate coefficient (krelaxH) for total nonreactive relaxation from the |04〉− state. The quasiclassical trajectory (QCT) method has been used to calculate the rate coefficient (kreac) for reaction between H atoms and H2O(|04〉−). Both the calculated rate coefficient (i.e., krelaxH+kreac) for total loss from H2O(|04〉−) and the calculated branching ratio, freac=kreac/(krelaxH+kreac)=0.38, are in quite good agreement with the experimental values.</abstract><doi>10.1063/1.1389304</doi><tpages>7</tpages></addata></record>
fulltext fulltext
identifier ISSN: 0021-9606
ispartof The Journal of chemical physics, 2001-09, Vol.115 (10), p.4586-4592
issn 0021-9606
1089-7690
language eng
recordid cdi_crossref_primary_10_1063_1_1389304
source American Institute of Physics (AIP) Journals; AIP Digital Archive
title The branching ratio between reaction and relaxation in the removal of H2O from its |04〉− vibrational state in collisions with H atoms
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-17T17%3A17%3A19IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-crossref&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=The%20branching%20ratio%20between%20reaction%20and%20relaxation%20in%20the%20removal%20of%20H2O%20from%20its%20%7C04%E3%80%89%E2%88%92%20vibrational%20state%20in%20collisions%20with%20H%20atoms&rft.jtitle=The%20Journal%20of%20chemical%20physics&rft.au=Barnes,%20Peter%20W.&rft.date=2001-09-08&rft.volume=115&rft.issue=10&rft.spage=4586&rft.epage=4592&rft.pages=4586-4592&rft.issn=0021-9606&rft.eissn=1089-7690&rft_id=info:doi/10.1063/1.1389304&rft_dat=%3Ccrossref%3E10_1063_1_1389304%3C/crossref%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true