{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,23]],"date-time":"2026-09-23T15:07:51Z","timestamp":1790176071257,"version":"4.1.0"},"reference-count":41,"publisher":"American Chemical Society (ACS)","issue":"5","license":[{"start":{"date-parts":[[2026,7,13]],"date-time":"2026-07-13T00:00:00Z","timestamp":1783900800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100003825","name":"Magyar Tudom?nyos Akad?mia","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100003825","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100011019","name":"Nemzeti Kutat?si Fejleszt?si ?s Innov?ci?s Hivatal","doi-asserted-by":"publisher","award":["150749"],"award-info":[{"award-number":["150749"]}],"id":[{"id":"10.13039\/501100011019","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100011019","name":"Nemzeti Kutat?si Fejleszt?si ?s Innov?ci?s Hivatal","doi-asserted-by":"publisher","award":["K-146759"],"award-info":[{"award-number":["K-146759"]}],"id":[{"id":"10.13039\/501100011019","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,9,23]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Here we report how specific reactant vibrational excitations impact the dynamics of the F\u2013 + NH2Cl reaction, with a special emphasis on the stereoselectivity of its SN2 channel, by performing quasi-classical trajectory simulations on a high-quality ab initio analytical potential energy surface. Exciting the N\u2013Cl stretching is found to enhance the SN2 reactivity the most, while N\u2013H stretching excitation is the most efficient in promoting proton transfer. The stereospecificity of the title reaction can be drastically manipulated by exciting (1) the umbrella vibration, which facilitates repeated inversion through a H-bonded entrance channel minimum and transition state, thereby making multi-inversion the dominant mechanism over a wide collision energy range, accompanied by the complete loss of stereoselectivity; (2) the N\u2013H stretching motion, which helps the H-bonded complex to form and thus lowers the inversion barrier around the N atom, thereby also promoting multi-inversion and racemization; and (3) the N\u2013Cl stretching mode, which favors direct Walden inversion over complex-forming multi-inversion, resulting in reinforced stereoselectivity. The excess vibrational energy mainly flows into the internal degrees of freedom of the products, and while making the SN2 reaction more direct, it has an overall moderate impact on proton-transfer dynamics.<\/jats:p>","DOI":"10.1021\/acsphyschemau.6c00092","type":"journal-article","created":{"date-parts":[[2026,7,13]],"date-time":"2026-07-13T12:34:17Z","timestamp":1783946057000},"page":"1299-1307","source":"Crossref","is-referenced-by-count":0,"title":["Controlling the Stereodynamics of the F\u2013 + NH2Cl SN2 Reaction by Vibrational Excitation:\nA Quasi-Classical Study"],"prefix":"10.1021","volume":"6","author":[{"given":"Deja\u0301n","family":"Dra\u0301gity","sequence":"first","affiliation":[{"name":"University of Szeged , , Rerrich Be\u0301la te\u0301r 1 , ,","place":["Szeged, Hungary, H-6720"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5136-4777","authenticated-orcid":true,"given":"Ga\u0301bor","family":"Czako\u0301","sequence":"additional","affiliation":[{"name":"University of Szeged , , Rerrich Be\u0301la te\u0301r 1 , ,","place":["Szeged, Hungary, H-6720"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1951-7619","authenticated-orcid":true,"given":"Do\u0301ra","family":"Papp","sequence":"additional","affiliation":[{"name":"University of Szeged , , Rerrich Be\u0301la te\u0301r 1 , ,","place":["Szeged, Hungary, H-6720"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,13]]},"reference":[{"key":"2026092310075592000_cit1","doi-asserted-by":"publisher","first-page":"2971","DOI":"10.1021\/j150658a011","article-title":"A Quasiclassical Trajectory Study\nof the State-to-State Dynamics of H + H2O \u2192 OH +\nH2","volume":"88","author":"Schatz","year":"1984","journal-title":"J. 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Phys. Chem.\nLett."},{"key":"2026092310075592000_cit18","doi-asserted-by":"publisher","DOI":"10.1126\/sciadv.aas9544","article-title":"Stretching\nVibration Is Spectator in Nucleophilic Substitution","volume":"4","author":"Stei","year":"2018","journal-title":"Sci. Adv."},{"key":"2026092310075592000_cit19","doi-asserted-by":"publisher","first-page":"4331","DOI":"10.1021\/acs.jpclett.0c01095","article-title":"Influence of Vibrational Excitation\non the Reaction of F\u2013 with CH3I: Spectator\nMode Behavior, Enhancement, and Suppression","volume":"11","author":"Michaelsen","year":"2020","journal-title":"J. Phys. Chem. Lett."},{"key":"2026092310075592000_cit20","doi-asserted-by":"publisher","first-page":"8166","DOI":"10.1039\/D2CP00685E","article-title":"Vibrational Mode-Specific Dynamics\nof the F\u2013 + CH3CH2Cl Multi-Channel\nReaction","volume":"24","author":"Tajti","year":"2022","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2026092310075592000_cit21","doi-asserted-by":"publisher","DOI":"10.1063\/5.0189561","article-title":"Vibrational\nMode-Specificity in the Dynamics of the\nOH\u2013 + CH3I Multi-Channel Reaction","volume":"160","author":"Tasi","year":"2024","journal-title":"J. Chem. Phys."},{"key":"2026092310075592000_cit22","doi-asserted-by":"publisher","first-page":"169","DOI":"10.1063\/1674-0068\/cjcp2203054","article-title":"Quantum Dynamics Study of OH\u2013 + CH3I\nReaction: Reaction Probability, Integral Cross Section, and Energy\nEfficacy","volume":"36","author":"Rao","year":"2023","journal-title":"Chin. J. Chem. Phys."},{"key":"2026092310075592000_cit23","doi-asserted-by":"publisher","first-page":"15818","DOI":"10.1039\/D4CP00417E","article-title":"First-Principles Mode-Specific\nReaction Dynamics","volume":"26","author":"Czako\u0301","year":"2024","journal-title":"Phys. Chem. Chem. 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Phys."},{"key":"2026092310075592000_cit30","doi-asserted-by":"publisher","first-page":"885","DOI":"10.1021\/acs.jpca.6b12240","article-title":"Activation Strain Analysis of SN2 Reactions\nat C, N, O, and F Centers","volume":"121","author":"Kubelka","year":"2017","journal-title":"J. Phys. Chem. A"},{"key":"2026092310075592000_cit31","doi-asserted-by":"publisher","first-page":"1886","DOI":"10.1021\/acs.jpca.7b11927","article-title":"Benchmark\nab Initio Characterization of the Complex\nPotential Energy Surfaces of the X\u2013 + NH2Y [X,Y = F, Cl, Br, I] Reactions","volume":"122","author":"Hajdu","year":"2018","journal-title":"J. Phys.\nChem. A"},{"key":"2026092310075592000_cit32","doi-asserted-by":"publisher","first-page":"5410","DOI":"10.1039\/D1SC00490E","article-title":"Facilitated Inversion Complicates the Stereodynamics\nof an SN2 Reaction at Nitrogen Center","volume":"12","author":"Papp","year":"2021","journal-title":"Chem. Sci."},{"key":"2026092310075592000_cit33","doi-asserted-by":"publisher","DOI":"10.1002\/cphc.202400365","article-title":"Computational\nStudies of Nucleophilic Substitution\nat Nitrogen Center: Reactions of NH2Cl with HO\u2013, CH3O\u2013 and C2H5O\u2013","volume":"25","author":"Dutta","year":"2024","journal-title":"ChemPhysChem"},{"key":"2026092310075592000_cit34","doi-asserted-by":"publisher","first-page":"1293","DOI":"10.1021\/acs.jpca.4c06805","article-title":"Unconventional\nPathways in Nitrogen-Centered SN2 Reactions: From Roundabout\nto Hydride Transfer","volume":"129","author":"Dutta","year":"2025","journal-title":"J. Phys. Chem. A"},{"key":"2026092310075592000_cit35","doi-asserted-by":"publisher","first-page":"51","DOI":"10.1021\/acs.jctc.9b01006","article-title":"Automating\nthe Development of High-Dimensional Reactive\nPotential Energy Surfaces with the Robosurfer Program System","volume":"16","author":"Gyo\u030bri","year":"2020","journal-title":"J. Chem. 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