On the photochemistry of IONO2 : absorption cross section (240-370 nm) and photolysis product yields at 248 nm
The absolute absorption cross section of IONO(2) was measured by the pulsed photolysis at 193 nm of a NO(2)/CF(3)I mixture, followed by time-resolved Fourier transform spectroscopy in the near-UV. The resulting cross section at a temperature of 296 K over the wavelength range from 240 to 370 nm is g...
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| creator | JOSEPH, D. M ASHWORTH, S. H PLANE, J. M. C |
| description | The absolute absorption cross section of IONO(2) was measured by the pulsed photolysis at 193 nm of a NO(2)/CF(3)I mixture, followed by time-resolved Fourier transform spectroscopy in the near-UV. The resulting cross section at a temperature of 296 K over the wavelength range from 240 to 370 nm is given by log(10)(sigma(IONO(2))/cm(2) molecule(-1)) = 170.4 - 3.773 lambda + 2.965 x 10(-2)lambda(2)- 1.139 x 10(-4)lambda(3) + 2.144 x 10(-7)lambda(4)- 1.587 x 10(-10)lambda(5), where lambda is in nm; the cross section, with 2sigma uncertainty, ranges from (6.5 +/- 1.9) x 10(-18) cm(2) at 240 nm to (5 +/- 3) x 10(-19) cm(2) at 350 nm, and is significantly lower than a previous measurement [J. C. Mössinger, D. M. Rowley and R. A. Cox, Atmos. Chem. Phys., 2002, 2, 227]. The photolysis quantum yields for IO and NO(3) production at 248 nm were measured using laser induced fluorescence of IO at 445 nm, and cavity ring-down spectroscopy of NO(3) at 662 nm, yielding phi(IO) |
| doi_str_mv | 10.1039/b709465e |
| format | Article |
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M ; ASHWORTH, S. H ; PLANE, J. M. C</creator><creatorcontrib>JOSEPH, D. M ; ASHWORTH, S. H ; PLANE, J. M. C</creatorcontrib><description>The absolute absorption cross section of IONO(2) was measured by the pulsed photolysis at 193 nm of a NO(2)/CF(3)I mixture, followed by time-resolved Fourier transform spectroscopy in the near-UV. The resulting cross section at a temperature of 296 K over the wavelength range from 240 to 370 nm is given by log(10)(sigma(IONO(2))/cm(2) molecule(-1)) = 170.4 - 3.773 lambda + 2.965 x 10(-2)lambda(2)- 1.139 x 10(-4)lambda(3) + 2.144 x 10(-7)lambda(4)- 1.587 x 10(-10)lambda(5), where lambda is in nm; the cross section, with 2sigma uncertainty, ranges from (6.5 +/- 1.9) x 10(-18) cm(2) at 240 nm to (5 +/- 3) x 10(-19) cm(2) at 350 nm, and is significantly lower than a previous measurement [J. C. Mössinger, D. M. Rowley and R. A. Cox, Atmos. Chem. Phys., 2002, 2, 227]. The photolysis quantum yields for IO and NO(3) production at 248 nm were measured using laser induced fluorescence of IO at 445 nm, and cavity ring-down spectroscopy of NO(3) at 662 nm, yielding phi(IO) </= 0.02 and phi(NO(3)) = 0.21 +/- 0.09. It is likely that photolysis to I + NO(3) is the only significant channel, as shown by accompanying quantum chemistry calculations. The low phi(NO(3)) is explained by the production of hot NO(3), most of which dissociates to NO(2) + O. In terms of atmospheric relevance, the noon photolysis frequency of J(IONO(2)) = (3.0 +/- 2.1) x 10(-3) s(-1) (40 degrees N, July) is fast enough to limit the effectiveness of IONO(2) as a daytime reservoir of iodine oxides, but the formation and subsequent photolysis of IONO(2) is very inefficient as an ozone-depleting cycle.</description><identifier>ISSN: 1463-9076</identifier><identifier>EISSN: 1463-9084</identifier><identifier>DOI: 10.1039/b709465e</identifier><identifier>PMID: 17957317</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Absorption - radiation effects ; Algorithms ; Atmosphere - chemistry ; Chemistry ; Exact sciences and technology ; General and physical chemistry ; Iodine - chemistry ; Iodine - radiation effects ; Models, Chemical ; Nitrates - chemistry ; Ozone - chemistry ; Photochemistry ; Photolysis - radiation effects ; Physical chemistry of induced reactions (with radiations, particles and ultrasonics) ; Quantum Theory ; Spectrophotometry - methods ; Temperature</subject><ispartof>Physical chemistry chemical physics : PCCP, 2007-01, Vol.9 (41), p.5599-5607</ispartof><rights>2007 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c331t-3cda0bfb77192afec0788bc5528f9221a42fe8beba1cdf7facbc72f532be58ea3</citedby><cites>FETCH-LOGICAL-c331t-3cda0bfb77192afec0788bc5528f9221a42fe8beba1cdf7facbc72f532be58ea3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,2829,27923,27924</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=19202897$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/17957317$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>JOSEPH, D. M</creatorcontrib><creatorcontrib>ASHWORTH, S. H</creatorcontrib><creatorcontrib>PLANE, J. M. C</creatorcontrib><title>On the photochemistry of IONO2 : absorption cross section (240-370 nm) and photolysis product yields at 248 nm</title><title>Physical chemistry chemical physics : PCCP</title><addtitle>Phys Chem Chem Phys</addtitle><description>The absolute absorption cross section of IONO(2) was measured by the pulsed photolysis at 193 nm of a NO(2)/CF(3)I mixture, followed by time-resolved Fourier transform spectroscopy in the near-UV. The resulting cross section at a temperature of 296 K over the wavelength range from 240 to 370 nm is given by log(10)(sigma(IONO(2))/cm(2) molecule(-1)) = 170.4 - 3.773 lambda + 2.965 x 10(-2)lambda(2)- 1.139 x 10(-4)lambda(3) + 2.144 x 10(-7)lambda(4)- 1.587 x 10(-10)lambda(5), where lambda is in nm; the cross section, with 2sigma uncertainty, ranges from (6.5 +/- 1.9) x 10(-18) cm(2) at 240 nm to (5 +/- 3) x 10(-19) cm(2) at 350 nm, and is significantly lower than a previous measurement [J. C. Mössinger, D. M. Rowley and R. A. Cox, Atmos. Chem. Phys., 2002, 2, 227]. The photolysis quantum yields for IO and NO(3) production at 248 nm were measured using laser induced fluorescence of IO at 445 nm, and cavity ring-down spectroscopy of NO(3) at 662 nm, yielding phi(IO) </= 0.02 and phi(NO(3)) = 0.21 +/- 0.09. It is likely that photolysis to I + NO(3) is the only significant channel, as shown by accompanying quantum chemistry calculations. The low phi(NO(3)) is explained by the production of hot NO(3), most of which dissociates to NO(2) + O. In terms of atmospheric relevance, the noon photolysis frequency of J(IONO(2)) = (3.0 +/- 2.1) x 10(-3) s(-1) (40 degrees N, July) is fast enough to limit the effectiveness of IONO(2) as a daytime reservoir of iodine oxides, but the formation and subsequent photolysis of IONO(2) is very inefficient as an ozone-depleting cycle.</description><subject>Absorption - radiation effects</subject><subject>Algorithms</subject><subject>Atmosphere - chemistry</subject><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>General and physical chemistry</subject><subject>Iodine - chemistry</subject><subject>Iodine - radiation effects</subject><subject>Models, Chemical</subject><subject>Nitrates - chemistry</subject><subject>Ozone - chemistry</subject><subject>Photochemistry</subject><subject>Photolysis - radiation effects</subject><subject>Physical chemistry of induced reactions (with radiations, particles and ultrasonics)</subject><subject>Quantum Theory</subject><subject>Spectrophotometry - methods</subject><subject>Temperature</subject><issn>1463-9076</issn><issn>1463-9084</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2007</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpF0E1LwzAYB_AgiptT8BNILso8VPPSNKk3Gb4Mhr3ouSRpwiptU5P00G9v3aaenjzw40-ePwCXGN1hRPN7xVGeZswcgTlOM5rkSKTHf2-ezcBZCJ8IIcwwPQUzzHPGKeZz0BUdjFsD-62LTm9NW4foR-gsXBdvBYEPUKrgfB9r10HtXQgwGL3bliRFCeUIdu0tlF21z2jGUAfYe1cNOsKxNk0VoIyQpGKC5-DEyiaYi8NcgI_np_fVa7IpXtarx02iKcUxobqSSFnFOc6JtEYjLoTSjBFhc0KwTIk1Qhklsa4st1IrzYlllCjDhJF0AW72udNHvgYTYjkdpk3TyM64IZSZSEnGMj7B5R7ubvPGlr2vW-nHEqPyp9vyt9uJXh0yB9Wa6h8eypzA9QHIoGVjvex0Hf5dThAROaffY_CAiw</recordid><startdate>20070101</startdate><enddate>20070101</enddate><creator>JOSEPH, D. M</creator><creator>ASHWORTH, S. H</creator><creator>PLANE, J. M. C</creator><general>Royal Society of Chemistry</general><scope>IQODW</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20070101</creationdate><title>On the photochemistry of IONO2 : absorption cross section (240-370 nm) and photolysis product yields at 248 nm</title><author>JOSEPH, D. M ; ASHWORTH, S. H ; PLANE, J. M. C</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c331t-3cda0bfb77192afec0788bc5528f9221a42fe8beba1cdf7facbc72f532be58ea3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2007</creationdate><topic>Absorption - radiation effects</topic><topic>Algorithms</topic><topic>Atmosphere - chemistry</topic><topic>Chemistry</topic><topic>Exact sciences and technology</topic><topic>General and physical chemistry</topic><topic>Iodine - chemistry</topic><topic>Iodine - radiation effects</topic><topic>Models, Chemical</topic><topic>Nitrates - chemistry</topic><topic>Ozone - chemistry</topic><topic>Photochemistry</topic><topic>Photolysis - radiation effects</topic><topic>Physical chemistry of induced reactions (with radiations, particles and ultrasonics)</topic><topic>Quantum Theory</topic><topic>Spectrophotometry - methods</topic><topic>Temperature</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>JOSEPH, D. M</creatorcontrib><creatorcontrib>ASHWORTH, S. H</creatorcontrib><creatorcontrib>PLANE, J. M. C</creatorcontrib><collection>Pascal-Francis</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Physical chemistry chemical physics : PCCP</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>JOSEPH, D. M</au><au>ASHWORTH, S. H</au><au>PLANE, J. M. C</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>On the photochemistry of IONO2 : absorption cross section (240-370 nm) and photolysis product yields at 248 nm</atitle><jtitle>Physical chemistry chemical physics : PCCP</jtitle><addtitle>Phys Chem Chem Phys</addtitle><date>2007-01-01</date><risdate>2007</risdate><volume>9</volume><issue>41</issue><spage>5599</spage><epage>5607</epage><pages>5599-5607</pages><issn>1463-9076</issn><eissn>1463-9084</eissn><abstract>The absolute absorption cross section of IONO(2) was measured by the pulsed photolysis at 193 nm of a NO(2)/CF(3)I mixture, followed by time-resolved Fourier transform spectroscopy in the near-UV. The resulting cross section at a temperature of 296 K over the wavelength range from 240 to 370 nm is given by log(10)(sigma(IONO(2))/cm(2) molecule(-1)) = 170.4 - 3.773 lambda + 2.965 x 10(-2)lambda(2)- 1.139 x 10(-4)lambda(3) + 2.144 x 10(-7)lambda(4)- 1.587 x 10(-10)lambda(5), where lambda is in nm; the cross section, with 2sigma uncertainty, ranges from (6.5 +/- 1.9) x 10(-18) cm(2) at 240 nm to (5 +/- 3) x 10(-19) cm(2) at 350 nm, and is significantly lower than a previous measurement [J. C. Mössinger, D. M. Rowley and R. A. Cox, Atmos. Chem. Phys., 2002, 2, 227]. The photolysis quantum yields for IO and NO(3) production at 248 nm were measured using laser induced fluorescence of IO at 445 nm, and cavity ring-down spectroscopy of NO(3) at 662 nm, yielding phi(IO) </= 0.02 and phi(NO(3)) = 0.21 +/- 0.09. It is likely that photolysis to I + NO(3) is the only significant channel, as shown by accompanying quantum chemistry calculations. The low phi(NO(3)) is explained by the production of hot NO(3), most of which dissociates to NO(2) + O. In terms of atmospheric relevance, the noon photolysis frequency of J(IONO(2)) = (3.0 +/- 2.1) x 10(-3) s(-1) (40 degrees N, July) is fast enough to limit the effectiveness of IONO(2) as a daytime reservoir of iodine oxides, but the formation and subsequent photolysis of IONO(2) is very inefficient as an ozone-depleting cycle.</abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><pmid>17957317</pmid><doi>10.1039/b709465e</doi><tpages>9</tpages></addata></record> |
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| subjects | Absorption - radiation effects Algorithms Atmosphere - chemistry Chemistry Exact sciences and technology General and physical chemistry Iodine - chemistry Iodine - radiation effects Models, Chemical Nitrates - chemistry Ozone - chemistry Photochemistry Photolysis - radiation effects Physical chemistry of induced reactions (with radiations, particles and ultrasonics) Quantum Theory Spectrophotometry - methods Temperature |
| title | On the photochemistry of IONO2 : absorption cross section (240-370 nm) and photolysis product yields at 248 nm |
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