{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,14]],"date-time":"2026-03-14T11:53:26Z","timestamp":1773489206647,"version":"3.50.1"},"reference-count":47,"publisher":"AIP Publishing","issue":"5","content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[1985,9,1]]},"abstract":"<jats:p>We report and compare two sets of thermal rate constants for the collinear reaction Cl+HBr\u2009\u2192\u2009HCl+Br, which is dominated by the n=0 vibrational state of reactants and the n=2 vibrational state of products. One set is based on converged multichannel quantal calculations carried out using hyperspherical coordinates. The other set is based on variational transition state theory (VTST) with a least-action (LA) ground-state (G) transmission coefficient (VTST\/LAG). The two sets of rate constants agree within a factor of 2.2 over the whole factor-of-12 temperature range (200\u20132400 K) studied. The error is comparable to what was found previously for the symmetric reaction Cl+HCl\u2032\u2009\u2192\u2009HCl+Cl\u2032, which is dominated by n=0 states of reactants and products. This indicates that the VTST\/LAG method is as applicable to reactions that proceed by tunneling into excited states as it is for ground-state-to-ground-state tunneling reactions. We also show that the VTST\/LA approximation provides useful accuracy for the rate constant of the collinear excited-state reaction Cl+HBr(n=1)\u2009\u2192\u2009HCl+Br.<\/jats:p>","DOI":"10.1063\/1.449318","type":"journal-article","created":{"date-parts":[[2002,7,26]],"date-time":"2002-07-26T13:08:03Z","timestamp":1027688883000},"page":"2252-2258","update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":92,"title":["Test of variational transition state theory and the least-action approximation for multidimensional tunneling probabilities against accurate quantal rate constants for a collinear reaction involving tunneling into an excited state"],"prefix":"10.1063","volume":"83","author":[{"given":"Bruce C.","family":"Garrett","sequence":"first","affiliation":[{"name":"Chemical Dynamics Corporation, Columbus, Ohio 43220"}]},{"given":"Najib","family":"Abusalbi","sequence":"additional","affiliation":[{"name":"Departments of Chemistry and Physics, University of Houston, Central Campus, Houston, Texas 77004"}]},{"given":"Donald J.","family":"Kouri","sequence":"additional","affiliation":[{"name":"Departments of Chemistry and Physics, University of Houston, Central Campus, Houston, Texas 77004"}]},{"given":"Donald G.","family":"Truhlar","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455"}]}],"member":"317","reference":[{"key":"2024021002192400700_r1","doi-asserted-by":"crossref","first-page":"200","DOI":"10.1021\/j100464a026","volume":"83","year":"1979","journal-title":"J. Phys. Chem."},{"key":"2024021002192400700_r1a","doi-asserted-by":"crossref","first-page":"682","DOI":"10.1021\/j100443a025","volume":"84","year":"1980","journal-title":"J. Phys. Chem."},{"key":"2024021002192400700_r1b","first-page":"4553","volume":"87","year":"1983","journal-title":"J. Phys. Chem."},{"key":"2024021002192400700_r1c","doi-asserted-by":"crossref","first-page":"4755","DOI":"10.1073\/pnas.76.10.4755","volume":"76","year":"1979","journal-title":"Proc. Natl. Acad. Sci. U.S.A."},{"key":"2024021002192400700_r2","doi-asserted-by":"crossref","first-page":"1730","DOI":"10.1021\/j100450a013","volume":"84","year":"1980","journal-title":"J. Phys. Chem."},{"key":"2024021002192400700_r3","doi-asserted-by":"crossref","first-page":"3019","DOI":"10.1021\/j150621a001","volume":"85","year":"1981","journal-title":"J. Phys. Chem."},{"key":"2024021002192400700_r3a","doi-asserted-by":"crossref","first-page":"2252","DOI":"10.1021\/j100209a021","volume":"86","year":"1982","journal-title":"J. Phys. Chem."},{"key":"2024021002192400700_r3b","first-page":"4554","volume":"87","year":"1983","journal-title":"J. Phys. Chem."},{"key":"2024021002192400700_r3c","doi-asserted-by":"crossref","first-page":"5955","DOI":"10.1063\/1.443866","volume":"77","year":"1982","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r4","doi-asserted-by":"crossref","first-page":"4400","DOI":"10.1063\/1.445323","volume":"78","year":"1983","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r5","doi-asserted-by":"crossref","first-page":"5981","DOI":"10.1063\/1.444613","volume":"78","year":"1983","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r6","doi-asserted-by":"crossref","first-page":"4931","DOI":"10.1063\/1.445586","volume":"79","year":"1983","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r7"},{"key":"2024021002192400700_r8","doi-asserted-by":"crossref","first-page":"1749","DOI":"10.1021\/j100450a014","volume":"84","year":"1980","journal-title":"J. Phys. Chem."},{"key":"2024021002192400700_r8a","doi-asserted-by":"crossref","first-page":"235","DOI":"10.1063\/1.439922","volume":"73","year":"1980","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r8b","doi-asserted-by":"crossref","first-page":"1721","DOI":"10.1063\/1.440308","volume":"73","year":"1980","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r8c","doi-asserted-by":"crossref","first-page":"3806","DOI":"10.1021\/j150625a019","volume":"85","year":"1981","journal-title":"J. Phys. Chem."},{"key":"2024021002192400700_r8d","doi-asserted-by":"crossref","first-page":"4986","DOI":"10.1063\/1.442845","volume":"76","year":"1982","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r8e","doi-asserted-by":"crossref","first-page":"777","DOI":"10.1063\/1.444829","volume":"78","year":"1983","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r8f","doi-asserted-by":"crossref","first-page":"3542","DOI":"10.1063\/1.448082","volume":"81","year":"1984","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r9","doi-asserted-by":"crossref","first-page":"309","DOI":"10.1063\/1.447386","volume":"81","year":"1984","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r10"},{"key":"2024021002192400700_r10a","doi-asserted-by":"crossref","first-page":"159","DOI":"10.1146\/annurev.pc.35.100184.001111","volume":"35","year":"1984","journal-title":"Annu. Rev. Phys. Chem."},{"key":"2024021002192400700_r11","first-page":"445","volume":"11","year":"1975","journal-title":"Teor. Eksp. Khin."},{"key":"2024021002192400700_r11a","first-page":"374","volume":"11","year":"1975","journal-title":"Theor. Exp. Chem."},{"key":"2024021002192400700_r11b","doi-asserted-by":"crossref","first-page":"85","DOI":"10.1016\/0301-0104(79)85106-X","volume":"36","year":"1979","journal-title":"Chem. Phys."},{"key":"2024021002192400700_r12","doi-asserted-by":"crossref","first-page":"2609","DOI":"10.1063\/1.435172","volume":"67","year":"1977","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r13","doi-asserted-by":"crossref","first-page":"99","DOI":"10.1063\/1.438959","volume":"72","year":"1980","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r14","doi-asserted-by":"crossref","first-page":"1790","DOI":"10.1063\/1.441267","volume":"74","year":"1981","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r15","doi-asserted-by":"crossref","first-page":"2244","DOI":"10.1021\/j100209a020","volume":"86","year":"1982","journal-title":"J. Phys. Chem."},{"key":"2024021002192400700_r16","doi-asserted-by":"crossref","first-page":"5621","DOI":"10.1063\/1.445442","volume":"78","year":"1983","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r16a","doi-asserted-by":"crossref","first-page":"1812","DOI":"10.1063\/1.446939","volume":"80","year":"1984","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r16b","doi-asserted-by":"crossref","first-page":"4181","DOI":"10.1063\/1.448205","volume":"81","year":"1984","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r16c","doi-asserted-by":"crossref","first-page":"507","DOI":"10.1016\/0009-2614(83)87024-9","volume":"101","year":"1983","journal-title":"Chem. Phys. Lett."},{"key":"2024021002192400700_r16d","doi-asserted-by":"crossref","first-page":"3962","DOI":"10.1063\/1.448135","volume":"81","year":"1984","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r17"},{"key":"2024021002192400700_r18","doi-asserted-by":"crossref","first-page":"5389","DOI":"10.1021\/j150644a017","volume":"87","year":"1983","journal-title":"J. Phys. Chem."},{"key":"2024021002192400700_r19"},{"key":"2024021002192400700_r20","doi-asserted-by":"crossref","first-page":"458","DOI":"10.1016\/0009-2614(84)85276-8","volume":"103","year":"1984","journal-title":"Chem. Phys. Lett."},{"key":"2024021002192400700_r21","doi-asserted-by":"crossref","first-page":"574","DOI":"10.1016\/0009-2614(82)83653-1","volume":"92","year":"1982","journal-title":"Chem. Phys. Lett."},{"key":"2024021002192400700_r22","doi-asserted-by":"crossref","first-page":"2232","DOI":"10.1063\/1.1677525","volume":"56","year":"1972","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r23","doi-asserted-by":"crossref","first-page":"3516","DOI":"10.1063\/1.444297","volume":"77","year":"1982","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r24"},{"key":"2024021002192400700_r25","doi-asserted-by":"crossref","first-page":"1052","DOI":"10.1021\/j100471a031","volume":"83","year":"1979","journal-title":"J. Phys. Chem."},{"key":"2024021002192400700_r25a","first-page":"4553","volume":"87","year":"1982","journal-title":"J. Phys. Chem."},{"key":"2024021002192400700_r25b","doi-asserted-by":"crossref","first-page":"3460","DOI":"10.1063\/1.439608","volume":"72","year":"1980","journal-title":"J. Chem. Phys."},{"key":"2024021002192400700_r26"}],"container-title":["The Journal of Chemical Physics"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.aip.org\/aip\/jcp\/article-pdf\/83\/5\/2252\/18954352\/2252_1_online.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.aip.org\/aip\/jcp\/article-pdf\/83\/5\/2252\/18954352\/2252_1_online.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,2,10]],"date-time":"2024-02-10T03:39:38Z","timestamp":1707536378000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.aip.org\/jcp\/article\/83\/5\/2252\/92017\/Test-of-variational-transition-state-theory-and"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[1985,9,1]]},"references-count":47,"journal-issue":{"issue":"5","published-print":{"date-parts":[[1985,9,1]]}},"URL":"https:\/\/doi.org\/10.1063\/1.449318","relation":{},"ISSN":["0021-9606","1089-7690"],"issn-type":[{"value":"0021-9606","type":"print"},{"value":"1089-7690","type":"electronic"}],"subject":[],"published-other":{"date-parts":[[1985,9,1]]},"published":{"date-parts":[[1985,9,1]]}}}