{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,12,31]],"date-time":"2025-12-31T04:53:06Z","timestamp":1767156786617,"version":"build-2238731810"},"reference-count":42,"publisher":"AIP Publishing","issue":"19","content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2011,5,21]]},"abstract":"<jats:p>The photodissociation dynamics of 3-bromo-1,1,1-trifluoro-2-propanol (BTFP) and 2-(bromomethyl) hexafluoro-2-propanol (BMHFP) have been studied at 234 nm, and the C\u2013Br bond dissociation investigated using resonance-enhanced multiphoton ionization coupled with time-of-flight mass spectrometer (REMPI-TOFMS). Br formation is a primary process and occurs on a repulsive surface involving the C\u2013Br bond of BTFP and BMHFP. Polarization dependent time-of-flight profiles were measured, and the translational energy distributions and recoil anisotropy parameters extracted using forward convolution fits. A strong polarization dependence of time-of-flight profiles suggest anisotropic distributions of the Br(2P3\/2) and Br(2P1\/2) fragments with anisotropy parameter, \u03b2, of respectively 0.5 \u00b1 0.2 and 1.2 \u00b1 0.2 for BTFP, and 0.4 \u00b1 0.1 and 1.0 \u00b1 0.3 for BMHFP. The measured velocity distributions consist of a single velocity component. The average translational energies for the Br(2P3\/2) and Br(2P1\/2) channels are 9.2 \u00b1 1.0 and 7.4 \u00b1 0.9 kcal\/mol for BTFP, and 15.4 \u00b1 1.8 and 15.1 \u00b1 2.0 kcal\/mol for BMHFP. The relative quantum yields of Br(2P3\/2) and Br(2P1\/2), which are 0.70 \u00b1 0.14 and 0.30 \u00b1 0.06 in BTFP and 0.81 \u00b1 0.16 and 0.19 \u00b1 0.04 in BMHFP, indicate that the yield of the former is predominant. The measured anisotropy parameters for the Br(2P3\/2) and Br(2P1\/2) channels suggest that the former channel has almost equal contributions from both the parallel and the perpendicular transitions, whereas the latter channel has a significant contribution from a parallel transition. Non-adiabatic curve crossing plays an important role in the C\u2013Br bond dissociation of both BTFP and BMHFP. The estimated curve crossing probabilities suggest a greater value in BTFP, which explains a greater observed value of the relative quantum yield of Br(2P1\/2) in this case.<\/jats:p>","DOI":"10.1063\/1.3591373","type":"journal-article","created":{"date-parts":[[2011,5,20]],"date-time":"2011-05-20T19:39:36Z","timestamp":1305920376000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":7,"title":["Photodissociation dynamics of 3-bromo-1,1,1-trifluoro-2-propanol and 2-(bromomethyl) hexafluoro-2-propanol at 234 nm: Resonance-enhanced multiphoton ionization detection of Br (2\n                    <i>P<\/i>\n                    <i>j<\/i>\n                    )"],"prefix":"10.1063","volume":"134","author":[{"given":"Yogesh N.","family":"Indulkar","sequence":"first","affiliation":[{"name":"Bhabha Atomic Research Centre 1 Radiation and Photochemistry Division, , Trombay, Mumbai 400 085, India"},{"name":"University of Pune 2 Department of Chemistry, , Ganeshkhind, Pune 411 007, India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ankur","family":"Saha","sequence":"additional","affiliation":[{"name":"Bhabha Atomic Research Centre 1 Radiation and Photochemistry Division, , Trombay, Mumbai 400 085, India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Hari P.","family":"Upadhyaya","sequence":"additional","affiliation":[{"name":"Bhabha Atomic Research Centre 1 Radiation and Photochemistry Division, , Trombay, Mumbai 400 085, India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Awadhesh","family":"Kumar","sequence":"additional","affiliation":[{"name":"Bhabha Atomic Research Centre 1 Radiation and Photochemistry Division, , Trombay, Mumbai 400 085, India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Suresh B.","family":"Waghmode","sequence":"additional","affiliation":[{"name":"University of Pune 2 Department of Chemistry, , Ganeshkhind, Pune 411 007, India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Prakash D.","family":"Naik","sequence":"additional","affiliation":[{"name":"Bhabha Atomic Research Centre 1 Radiation and Photochemistry Division, , Trombay, Mumbai 400 085, India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Parma Nand","family":"Bajaj","sequence":"additional","affiliation":[{"name":"Bhabha Atomic Research Centre 1 Radiation and Photochemistry Division, , Trombay, Mumbai 400 085, India"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"317","published-online":{"date-parts":[[2011,5,20]]},"reference":[{"key":"2023080405594065800_c1","doi-asserted-by":"publisher","first-page":"215","DOI":"10.1029\/GL002i006p00215","volume":"2","year":"1975","journal-title":"Geophys. 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