{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,14]],"date-time":"2025-10-14T00:59:24Z","timestamp":1760403564068,"version":"build-2065373602"},"reference-count":107,"publisher":"Wiley","issue":"3","license":[{"start":{"date-parts":[[2005,3,4]],"date-time":"2005-03-04T00:00:00Z","timestamp":1109894400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPhysChem"],"published-print":{"date-parts":[[2005,3,11]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p><jats:italic>Vibrationally excited O<jats:sub>2<\/jats:sub>, OH, and HO<jats:sub>2<\/jats:sub> species have been suggested (<\/jats:italic>J. Phys. Chem. A <jats:italic><jats:bold>2004<\/jats:bold>,<\/jats:italic> 108<jats:italic>, 758) to provide clues for explaining the \u201cozone deficit problem\u201d and \u201cHO<\/jats:italic><jats:sub>x<\/jats:sub> <jats:italic>dilemma\u201d in the middle atmosphere under conditions of local thermodynamic disequilibrium (LTD), but the question arises of how much LTD will affect the title ozone sink reactions. Besides providing novel kinetic results, it is shown that LTD tends to disfavor ozone depletion relative to traditional atmospheric modeling under Boltzmann equilibration, which is partly due to competition between the various reactive channels. The calculations also suggest that the title LTD processes can be important sources of highly vibrationally excited O<jats:sub>2<\/jats:sub> in the middle atmosphere. Moreover, LTD is shown to offer an explanation for the fact that some down revision of the O+HO<jats:sub>2<\/jats:sub> rate constant, or the ratio of the O+HO<jats:sub>2<\/jats:sub> to O+OH rate constants, is required to improve agreement between the predictions of traditional modeling and observation. This, in turn, provides significant evidence supporting LTD at such altitudes.<\/jats:italic><\/jats:p>","DOI":"10.1002\/cphc.200400335","type":"journal-article","created":{"date-parts":[[2005,3,4]],"date-time":"2005-03-04T07:19:16Z","timestamp":1109920756000},"page":"453-465","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":19,"title":["What are the Implications of Nonequilibrium in the O+OH and O+HO<sub>2<\/sub> Reactions?"],"prefix":"10.1002","volume":"6","author":[{"given":"A. J. C.","family":"Varandas","sequence":"first","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2005,3,4]]},"reference":[{"volume-title":"Atmospheric Change","year":"1993","author":"Graedel T. E.","key":"e_1_2_7_1_2"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.265.5180.1817"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.466997"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1029\/93GL03149"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/1439-7641(20020517)3:5<433::AID-CPHC433>3.0.CO;2-O"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp036321p"},{"key":"e_1_2_7_7_2","doi-asserted-by":"publisher","DOI":"10.1039\/fd9950000229"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/0301-0104(93)80230-7"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.468770"},{"key":"e_1_2_7_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(95)00698-4"},{"key":"e_1_2_7_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0301-0104(96)00344-8"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0009-2614(97)00838-5"},{"key":"e_1_2_7_13_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0301-0104(98)00164-5"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0009-2614(98)00406-0"},{"key":"e_1_2_7_15_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.475751"},{"key":"e_1_2_7_16_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0009-2614(98)00347-9"},{"key":"e_1_2_7_17_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1288370"},{"key":"e_1_2_7_18_2","doi-asserted-by":"publisher","DOI":"10.1080\/01442350050020888"},{"key":"e_1_2_7_19_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.479618"},{"key":"e_1_2_7_20_2","doi-asserted-by":"publisher","DOI":"10.1029\/JD092iD03p03067"},{"key":"e_1_2_7_21_2","doi-asserted-by":"publisher","DOI":"10.1029\/92JD01912"},{"key":"e_1_2_7_22_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.265.5180.1831"},{"key":"e_1_2_7_23_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.268.5211.705"},{"key":"e_1_2_7_24_2","doi-asserted-by":"publisher","DOI":"10.1029\/97GL00921"},{"key":"e_1_2_7_25_2","doi-asserted-by":"publisher","DOI":"10.1029\/2000GL011698"},{"key":"e_1_2_7_26_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.277.5334.1967"},{"key":"e_1_2_7_27_2","doi-asserted-by":"publisher","DOI":"10.1029\/98JD00432"},{"key":"e_1_2_7_28_2","doi-asserted-by":"publisher","DOI":"10.1029\/1998GL900009"},{"key":"e_1_2_7_29_2","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(95)01384-9"},{"key":"e_1_2_7_30_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp961863a"},{"key":"e_1_2_7_31_2","unstructured":"One may infer from previous dynamics studies[29 30]on the reaction H+ArO2\u2192Ar+HO2that HO2is possibly formed in a highly vibrationally excited state but it would be interesting to perform similar studies with the active species O2acting itself also as the chaperon which could be done by employing our recently reported double many\u2010body expansion (DMBE) potential energy surface[32]for the electronic ground state of HO4."},{"key":"e_1_2_7_32_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0009-2614(00)01222-7"},{"key":"e_1_2_7_33_2","unstructured":"kndenotes the rate constant for reaction (n)."},{"key":"e_1_2_7_34_2","unstructured":"Note that the middle of Equation (41) of ref. [6] has a misprint: the symbol \u2248 preceding [O3]\/[M] should obviously be eliminated."},{"key":"e_1_2_7_35_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp010291d"},{"key":"e_1_2_7_36_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0009-2614(01)00314-1"},{"key":"e_1_2_7_37_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp0203245"},{"key":"e_1_2_7_38_2","doi-asserted-by":"publisher","DOI":"10.1039\/B203101A"},{"key":"e_1_2_7_39_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp022483u"},{"key":"e_1_2_7_40_2","doi-asserted-by":"publisher","DOI":"10.1016\/0301-0104(88)85082-1"},{"key":"e_1_2_7_41_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp982436v"},{"key":"e_1_2_7_42_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0009-2614(98)00925-7"},{"key":"e_1_2_7_43_2","unstructured":"W. L. Hase MERCURY: a general Monte Carlo classical trajectory computer program QCPE#453. An updated version of this code is VENUS96:"},{"key":"e_1_2_7_43_3","first-page":"43","volume":"16","author":"Hase W. L.","year":"1996","journal-title":"QCPE Bull"},{"key":"e_1_2_7_44_2","doi-asserted-by":"publisher","DOI":"10.1021\/j100384a019"},{"key":"e_1_2_7_45_2","doi-asserted-by":"publisher","DOI":"10.1080\/002689797171607"},{"key":"e_1_2_7_46_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0009-2614(00)01432-9"},{"key":"e_1_2_7_47_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.462755"},{"key":"e_1_2_7_48_2","unstructured":"Note that only odd rotational states are allowed if OH is considered to belong to Hund's case (b).[106]"},{"key":"e_1_2_7_49_2","unstructured":"Strictly speaking this implies nonvariation with time a prerequisite that cannot obviously be warranted in our definition."},{"key":"e_1_2_7_50_2","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(85)85312-4"},{"key":"e_1_2_7_51_2","unstructured":"P. C. Cosby private communication July2002."},{"key":"e_1_2_7_52_2","unstructured":"This effective rotational distribution has in turn been obtained by weighting the rotational distributions actually reported by Cosby[51]for the six OH Meinel bands (4\u20130 5\u20131 6\u20131 7\u20132 8\u20133 9\u20134) with the appropriate weights given by the nascent vibrational distribution of Ohoyama et al.[50]Note that the Cosby distributions represent season\u2010averaged values for OH in the nightglow (i.e. created by the H+O3reaction) subject to some collisional relaxation before emitting. This is most likely responsible[51]for the two\u2010temperature rotational distributions observed in the nightglow data: a low temperature (\u2248200 K) in the rapidly relaxed lower rotational levels (j\u2032<5) and a much higher apparent temperature in the slowly relaxed higher rotational levels; see Figure 4\u2009a of ref. [39]. See also ref. [6]."},{"volume-title":"Chemistry of Atmospheres, 3rd","year":"2002","author":"Wayne R. P.","key":"e_1_2_7_53_2"},{"key":"e_1_2_7_54_2","doi-asserted-by":"publisher","DOI":"10.1039\/b010149o"},{"key":"e_1_2_7_55_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0009-2614(01)00364-5"},{"key":"e_1_2_7_56_2","unstructured":"Note that the threshold translational energy[32]for the OH(v\u2032=0)+O3reaction isEth=1.056 kcal\u2009mol\u22121 which implies that it cannot occur for collisional energies smaller thanEth. Of course this does not mean that reaction cannot occur at an equivalent translational temperature of 354.3 K. The vibrational population of OH predicted from the steady\u2010state distribution is very small forv\u2032=0 therefore such an issue may here be safely ignored."},{"key":"e_1_2_7_57_2","unstructured":"This is an approximate sampling method due to the significant anharmonicity of the HO2and O3potential energy surfaces."},{"key":"e_1_2_7_58_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.469884"},{"key":"e_1_2_7_59_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp970960g"},{"key":"e_1_2_7_60_2","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(94)00620-2"},{"key":"e_1_2_7_61_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.466544"},{"key":"e_1_2_7_62_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.470430"},{"key":"e_1_2_7_63_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.472668"},{"key":"e_1_2_7_64_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.470853"},{"key":"e_1_2_7_65_2","doi-asserted-by":"publisher","DOI":"10.1039\/a608119c"},{"key":"e_1_2_7_66_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.475516"},{"key":"e_1_2_7_67_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.450758"},{"key":"e_1_2_7_68_2","doi-asserted-by":"publisher","DOI":"10.1021\/j100326a059"},{"key":"e_1_2_7_69_2","doi-asserted-by":"publisher","DOI":"10.1016\/0301-0104(88)87073-3"},{"key":"e_1_2_7_70_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.457985"},{"key":"e_1_2_7_71_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.463934"},{"key":"e_1_2_7_72_2","doi-asserted-by":"publisher","DOI":"10.1016\/0301-0104(93)80137-X"},{"key":"e_1_2_7_73_2","doi-asserted-by":"publisher","DOI":"10.1039\/ft9949002189"},{"key":"e_1_2_7_74_2","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(84)85755-3"},{"key":"e_1_2_7_75_2","doi-asserted-by":"publisher","DOI":"10.1029\/97JA01622"},{"key":"e_1_2_7_76_2","unstructured":"Recall that the classical barrier height for O\u2010attacking the H end of OH is about 13.4 kcal\u2009mol\u22121."},{"key":"e_1_2_7_77_2","unstructured":"The numbers are quoted with a fixed number of digits along the paper; however this was done only for convenience and by no means invalidates the accuracy expressed by the error bars when given."},{"key":"e_1_2_7_78_2","unstructured":"We denote by (v\u2032\u2032 j\u2032\u2032) the vibrational\u2013rotational state of the OH radicals either formed reactively or nonreactively."},{"key":"e_1_2_7_79_2","doi-asserted-by":"publisher","DOI":"10.1086\/316272"},{"key":"e_1_2_7_80_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.cplett.2004.08.023"},{"key":"e_1_2_7_81_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.555918"},{"key":"e_1_2_7_82_2","first-page":"353","volume":"84","author":"Varandas A. 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