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All possible fragmentation pathways, namely, CH2Cl + h\u03bd \u2192 CH2 + Cl, HCCl + H, and CCl + H2, have been analyzed. The potential-energy curves of the ground and several excited electronic states along the corresponding dissociating bond distance of each pathway have been calculated. Inclusion of the spin\u2013orbit couplings is found to be crucial because it strongly determines the shape of the curves of the different excited states and, therefore, their photodissociation dynamics behavior. Analysis of the potential curves indicates that the pathways producing CH2 + Cl and HCCl + H can occur through a fast direct dissociation mechanism, while the pathway leading to CCl + H2 involves much slower dissociation mechanisms such as internal conversion between electronic states, predissociation, or tunneling through exit barriers. The main implications are that the two faster channels are predicted to be dominant, while the slower pathway is expected to be very unlikely and rather irrelevant. Appreciable actinic fluxes of solar irradiation are available at stratospheric altitudes where ozone is abundant, in the wavelength range where absorption of the first low-lying excited states of CH2Cl has been observed experimentally. Our results show that in this excitation energy range, the above-mentioned two dominant dissociation pathways are open and then could contribute to stratospheric ozone depletion.<\/jats:p>","DOI":"10.1063\/5.0243800","type":"journal-article","created":{"date-parts":[[2024,12,18]],"date-time":"2024-12-18T13:20:23Z","timestamp":1734528023000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":2,"title":["Photodissociation of the CH2Cl radical: A high-level <i>ab\u00a0initio<\/i> study"],"prefix":"10.1063","volume":"161","author":[{"ORCID":"https:\/\/orcid.org\/0009-0002-3097-4589","authenticated-orcid":false,"given":"F.","family":"Charfeddine","sequence":"first","affiliation":[{"name":"Laboratoire de Spectroscopie Atomique, Mol\u00e9culaire et Applications-LSAMA LR01ES09, Facult\u00e9 des Sciences de Tunis, Universit\u00e9 de Tunis El Manar 1 , 2092 Tunis,","place":["Tunisia"]},{"name":"Instituto de F\u00edsica Fundamental, Consejo Superior de Investigaciones Cient\u00edficas 2 , Serrano 123, 28006 Madrid,","place":["Spain"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4462-829X","authenticated-orcid":false,"given":"O.","family":"Yazidi","sequence":"additional","affiliation":[{"name":"Laboratoire de Spectroscopie Atomique, Mol\u00e9culaire et Applications-LSAMA LR01ES09, Facult\u00e9 des Sciences de Tunis, Universit\u00e9 de Tunis El Manar 1 , 2092 Tunis,","place":["Tunisia"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0471-5658","authenticated-orcid":false,"given":"A.","family":"Zanchet","sequence":"additional","affiliation":[{"name":"Instituto de F\u00edsica Fundamental, Consejo Superior de Investigaciones Cient\u00edficas 2 , Serrano 123, 28006 Madrid,","place":["Spain"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0777-2375","authenticated-orcid":false,"given":"L.","family":"Ba\u00f1ares","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica F\u00edsica, Facultad de Ciencias Qu\u00edmicas, Universidad Complutense de Madrid (Unidad Asociada I+D+i CSIC) 3 , 28040 Madrid,","place":["Spain"]},{"name":"Instituto Madrile\u00f1o de Estudios Avanzados en Nanociencia (IMDEA-Nanoscience) 4 , 28049 Madrid,","place":["Spain"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1214-2132","authenticated-orcid":false,"given":"A.","family":"Garc\u00eda-Vela","sequence":"additional","affiliation":[{"name":"Instituto de F\u00edsica Fundamental, Consejo Superior de Investigaciones Cient\u00edficas 2 , Serrano 123, 28006 Madrid,","place":["Spain"]}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"317","published-online":{"date-parts":[[2024,12,18]]},"reference":[{"volume-title":"Reactive Intermediate Chemistry","year":"2004","key":"2024121813201867400_c1"},{"volume-title":"Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications","year":"1999","key":"2024121813201867400_c2"},{"key":"2024121813201867400_c3","first-page":"79","article-title":"Atmospheric photochemistry of alternative halocarbons","volume-title":"Advances in Photochemistry","year":"1995"},{"key":"2024121813201867400_c4","doi-asserted-by":"publisher","first-page":"4035","DOI":"10.1021\/cr5006638","article-title":"Tropospheric halogen chemistry: Sources, cycling, and impacts","volume":"115","year":"2015","journal-title":"Chem. 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