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However, the origin of the chemo\u2010 and regioselectivities of fluorobenzenes remains unexplained because of the experimental limitations in resolving the excited\u2010state structures on ultrafast timescales. The computational cost of multiconfigurational nonadiabatic molecular dynamics simulations is also currently cost\u2010prohibitive. We now provide high\u2010fidelity structural information and reaction outcome predictions with machine\u2010learning\u2010accelerated photodynamics simulations of a series of fluorobenzenes, C<jats:sub>6<\/jats:sub>F<jats:sub>6\u2010n<\/jats:sub>H<jats:sub>n<\/jats:sub>, n=0\u20133, to study their S<jats:sub>1<\/jats:sub>\u2192S<jats:sub>0<\/jats:sub> decay in 4\u2005ns. We trained neural networks with XMS\u2010CASPT2(6,7)\/aug\u2010cc\u2010pVDZ calculations, which reproduced the S<jats:sub>1<\/jats:sub> absorption features with mean absolute errors of 0.04\u2005eV (&lt;2\u2005nm). The predicted nonradiative decay constants for C<jats:sub>6<\/jats:sub>F<jats:sub>4<\/jats:sub>H<jats:sub>2<\/jats:sub>, C<jats:sub>6<\/jats:sub>F<jats:sub>6<\/jats:sub>, C<jats:sub>6<\/jats:sub>F<jats:sub>3<\/jats:sub>H<jats:sub>3<\/jats:sub>, and C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>H are 116, 60, 28, and 12\u2005ps, respectively, in broad qualitative agreement with the experiments. Our calculations show that a pseudo Jahn\u2013Teller distortion of fluorinated benzenes leads to an S<jats:sub>1<\/jats:sub> local\u2010minimum region that extends the excited\u2010state lifetimes of fluorobenzenes. The pseudo Jahn\u2013Teller distortions reduce when fluorination decreases. Our analysis of the S<jats:sub>1<\/jats:sub> dynamics shows that the pseudo\u2010Jahn\u2013Teller distortions promote an excited\u2010state <jats:italic>cis\u2010trans<\/jats:italic> isomerization of a \u03c0<jats:sub>C\u2010C<\/jats:sub> bond. We characterized the surface hopping points from our NAMD simulations and identified instantaneous nuclear momentum as a factor that promotes the electrocyclizations.<\/jats:p>","DOI":"10.1002\/chem.202200651","type":"journal-article","created":{"date-parts":[[2022,4,26]],"date-time":"2022-04-26T22:14:27Z","timestamp":1651011267000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":17,"title":["Excited\u2010State Distortions Promote the Photochemical 4\u03c0\u2010Electrocyclizations of Fluorobenzenes via Machine Learning Accelerated Photodynamics Simulations"],"prefix":"10.1002","volume":"28","author":[{"given":"Jingbai","family":"Li","sequence":"first","affiliation":[{"name":"Department of Chemistry and Chemical Biology Northeastern University  Boston MA 02115 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8418-3638","authenticated-orcid":false,"given":"Steven A.","family":"Lopez","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Chemical Biology Northeastern University  Boston MA 02115 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,5,25]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201901230"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00723"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201901143"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.0c01212"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.trechm.2021.1010.1007"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/aenm.201601622"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/marc.201900413"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1070\/RC1991v060n05ABEH001088"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00372a050"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr500523x"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41557-020-00608-8"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01006a058"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00055a042"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1SC00775K"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00961a055"},{"key":"e_1_2_8_16_1","first-page":"313","author":"Camaggi G.","year":"1966","journal-title":"Chem. 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