{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,23]],"date-time":"2026-10-23T19:53:31Z","timestamp":1792785211159,"version":"4.5.0"},"reference-count":37,"publisher":"AIP Publishing","issue":"14","funder":[{"name":"US Department of Defense, Office of Naval Research","award":["N00014-22-1-2661"],"award-info":[{"award-number":["N00014-22-1-2661"]}],"id":[{"id":"https:\/\/ror.org\/00rk2pe57","id-type":"ROR","asserted-by":"crossref"}]},{"DOI":"10.13039\/501100003593","name":"Conselho Nacional de Desenvolvimento Cient\u00edfico e Tecnol\u00f3gico","doi-asserted-by":"publisher","award":["305211\/2024-2"],"award-info":[{"award-number":["305211\/2024-2"]}],"id":[{"id":"10.13039\/501100003593","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2026,10,14]]},"abstract":"<jats:p>The recently developed semiclassical theory of nonadiabatic energy transfer in three-dimensional atom-atom collisions is extended to predict the electronic excitation and quenching in atom\u2013molecule collisions. The two main assumptions of the present model are (i) the critical role of orbiting collisions, which result in multiple crossings of the seam between the potential energy surfaces in a resonance state of the atom-diatom complex, and (ii) a statistical distribution of the atom\u2013diatom complex over the resonance vibrational states. The cross sections and rate coefficients predicted by the model are compared with quasi-classical trajectory\/surface hopping calculations and quantum wavepacket scattering for N(2D) + N2 \u2194 N(4S) + N2, N(2D) + CO \u2194 N(4S) + CO, and C(1D) + N2 \u2194 C(3P) + N2, using the ab\u00a0initio potential energy surfaces and nonadiabatic couplings, and with the experimental data where available. The quenching rate coefficients predicted by the semiclassical model are in good overall agreement with the quasiclassical trajectory calculations and quantum scattering. The semiclassical excitation rate coefficient for N + N2 is in good agreement with that obtained from quasiclassical trajectory calculations with Landau\u2013Zener surface hopping (QCT-LZ) using the detailed balance, over a wide range of temperatures. Both the semiclassical and QCT-LZ excitation rates at high temperatures are significantly higher compared to those predicted by QCT with coherent switches\/decay of mixing with zero-point energy correction and by quantum scattering. The approximate analytic expressions for the semiclassical transition probabilities and rate coefficients have been obtained.<\/jats:p>","DOI":"10.1063\/5.0358052","type":"journal-article","created":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T11:01:31Z","timestamp":1791975691000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":0,"title":["Semiclassical model of nonadiabatic energy transfer in atom-molecule collisions"],"prefix":"10.1063","volume":"165","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-6311-3940","authenticated-orcid":false,"given":"Igor V.","family":"Adamovich","sequence":"first","affiliation":[{"name":"Department of Mechanical and Aerospace Engineering, The Ohio State University 1 , Columbus, Ohio 43210,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4184-2437","authenticated-orcid":false,"given":"Breno R. L.","family":"Galv\u00e3o","sequence":"additional","affiliation":[{"name":"Centro Federal de Educa\u00e7\u00e3o Tecnol\u00f3gica de Minas Gerais 2 , Belo Horizonte, Minas Gerais 30421-169,","place":["Brazil"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4448-1216","authenticated-orcid":false,"given":"Timothy T.","family":"Aiken","sequence":"additional","affiliation":[{"name":"Center for National Security Initiatives, University of Colorado 3 , Boulder, Colorado 80309,","place":["USA"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2026,10,14]]},"reference":[{"issue":"5","key":"2026101407012993900_c1","doi-asserted-by":"publisher","first-page":"436","DOI":"10.1134\/s1063780x09050092","article-title":"Associative ionization reactions involving excited atoms in nitrogen plasma","volume":"35","year":"2009","journal-title":"Plasma Phys. Rep."},{"issue":"1","key":"2026101407012993900_c2","doi-asserted-by":"publisher","first-page":"154","DOI":"10.2514\/1.t5735","article-title":"Measurement of radiative nonequilibrium for air shocks between 7 and 9 km\/s","volume":"34","year":"2020","journal-title":"J.\u00a0Thermophys. Heat Transfer"},{"issue":"11\u201312","key":"2026101407012993900_c3","doi-asserted-by":"publisher","first-page":"1266","DOI":"10.1016\/j.sab.2009.10.003","article-title":"Effects of oxygen addition to argon glow discharges: A hybrid Monte Carlo-fluid modeling investigation","volume":"64","year":"2009","journal-title":"Spectrochim. Acta, Part B"},{"issue":"14","key":"2026101407012993900_c4","doi-asserted-by":"publisher","first-page":"2292","DOI":"10.1021\/jz401012t","article-title":"Electronic quenching of N(2D) by N2: Theoretical predictions, comparison with experimental rate constants, and impact on atmospheric modeling","volume":"4","year":"2013","journal-title":"J.\u00a0Phys. Chem. Lett."},{"issue":"5","key":"2026101407012993900_c5","doi-asserted-by":"publisher","first-page":"1872","DOI":"10.1021\/ct500085q","article-title":"Electronic quenching in N(2D) + N2 collisions: A state-specific analysis via surface hopping dynamics","volume":"10","year":"2014","journal-title":"J.\u00a0Chem. Theory Comput."},{"issue":"18","key":"2026101407012993900_c6","doi-asserted-by":"publisher","first-page":"184302","DOI":"10.1063\/1.4919743","article-title":"The effect of intersystem crossings in N(2D) + H2 collisions","volume":"142","year":"2015","journal-title":"J.\u00a0Chem. Phys."},{"issue":"15","key":"2026101407012993900_c7","doi-asserted-by":"publisher","first-page":"154301","DOI":"10.1063\/5.0260316","article-title":"Electronic quenching of N(2D) in collision with CO(1\u03a3+) via spin-forbidden transitions","volume":"162","year":"2025","journal-title":"J.\u00a0Chem. Phys."},{"issue":"23","key":"2026101407012993900_c8","doi-asserted-by":"publisher","first-page":"15656","DOI":"10.1039\/d3cp01429k","article-title":"Quantum and semiclassical studies of nonadiabatic electronic transitions between N(4S) and N(2D) by collisions with N2","volume":"25","year":"2023","journal-title":"Phys. Chem. Chem. Phys."},{"issue":"14","key":"2026101407012993900_c9","doi-asserted-by":"publisher","first-page":"3190","DOI":"10.1021\/acs.jpca.3c00893","article-title":"Quantum and semiclassical dynamics of nonadiabatic electronic excitation of C(3P) to C(1D) by hyperthermal collisions with N2","volume":"127","year":"2023","journal-title":"J.\u00a0Phys. Chem. A"},{"issue":"17","key":"2026101407012993900_c10","doi-asserted-by":"publisher","first-page":"8645","DOI":"10.1039\/c8cp07171c","article-title":"First-principles dynamics of collisional intersystem crossing: Resonance enhanced quenching of C(1D) by N2","volume":"21","year":"2019","journal-title":"Phys. Chem. Chem. Phys."},{"issue":"12","key":"2026101407012993900_c11","doi-asserted-by":"publisher","first-page":"10630","DOI":"10.1063\/1.467877","article-title":"Theory of nonadiabatic transition for general two-state curve crossing problems. I. Nonadiabatic tunneling case","volume":"101","year":"1994","journal-title":"J.\u00a0Chem. Phys."},{"issue":"19","key":"2026101407012993900_c12","doi-asserted-by":"publisher","first-page":"7448","DOI":"10.1063\/1.469057","article-title":"Theory of nonadiabatic transition for general two-state curve crossing problems. II. Landau\u2013Zener case","volume":"102","year":"1995","journal-title":"J.\u00a0Chem. Phys."},{"issue":"19","key":"2026101407012993900_c13","doi-asserted-by":"publisher","first-page":"194101","DOI":"10.1063\/5.0209058","article-title":"Semiclassical analytic theory of electronic energy transfer in 3-D atomic collisions","volume":"160","year":"2024","journal-title":"J.\u00a0Chem. Phys."},{"issue":"22","key":"2026101407012993900_c14","doi-asserted-by":"publisher","first-page":"224121","DOI":"10.1063\/5.0305416","article-title":"Semiclassical analytic theory of multi-channel electronic energy transfer in nonadiabatic atomic collisions","volume":"163","year":"2025","journal-title":"J.\u00a0Chem. Phys."},{"issue":"10","key":"2026101407012993900_c15","doi-asserted-by":"publisher","first-page":"103512","DOI":"10.1063\/5.0294530","article-title":"Three-temperature collisional-radiative model of ionization and recombination in hypersonic air plasmas","volume":"32","year":"2025","journal-title":"Phys. Plasmas"},{"issue":"52","key":"2026101407012993900_c16","doi-asserted-by":"publisher","first-page":"14424","DOI":"10.1021\/jp903719h","article-title":"Accurate double many-body expansion potential energy surface for N3(4A\u2033) from correlation scaled ab\u00a0initio energies with extrapolation to the complete basis set limit","volume":"113","year":"2009","journal-title":"J.\u00a0Phys. Chem. A"},{"issue":"44","key":"2026101407012993900_c17","doi-asserted-by":"publisher","first-page":"12390","DOI":"10.1021\/jp2073396","article-title":"Ab initio based double-sheeted DMBE potential energy surface for N3(2A\u2033) and exploratory dynamics calculations","volume":"115","year":"2011","journal-title":"J.\u00a0Phys. Chem. A"},{"issue":"22","key":"2026101407012993900_c18","doi-asserted-by":"publisher","first-page":"22A515","DOI":"10.1063\/1.4737858","article-title":"N(4S\/2D) + N2: Accurate ab\u00a0initio-based DMBE potential energy surfaces and surface-hopping dynamics","volume":"137","year":"2012","journal-title":"J.\u00a0Chem. Phys."},{"issue":"1","key":"2026101407012993900_c19","doi-asserted-by":"publisher","first-page":"014106","DOI":"10.1063\/1.1804497","article-title":"High-level ab\u00a0initio studies of unimolecular dissociation of the ground-state N3 radical","volume":"122","year":"2005","journal-title":"J.\u00a0Chem. Phys."},{"issue":"16","key":"2026101407012993900_c20","doi-asserted-by":"publisher","first-page":"7658","DOI":"10.1063\/1.1793991","article-title":"Coherent switching with decay of mixing: An improved treatment of electronic coherence for non-Born\u2013Oppenheimer trajectories","volume":"121","year":"2004","journal-title":"J.\u00a0Chem. Phys."},{"issue":"2","key":"2026101407012993900_c21","doi-asserted-by":"publisher","first-page":"101","DOI":"10.1021\/ar040206v","article-title":"Non-Born\u2013Oppenheimer molecular dynamics","volume":"39","year":"2006","journal-title":"Acc. Chem. Res."},{"issue":"2","key":"2026101407012993900_c22","doi-asserted-by":"publisher","first-page":"1061","DOI":"10.1063\/1.459170","article-title":"Molecular dynamics with electronic transitions","volume":"93","year":"1990","journal-title":"J.\u00a0Chem. Phys."},{"issue":"1","key":"2026101407012993900_c23","doi-asserted-by":"publisher","first-page":"014104","DOI":"10.1063\/5.0215553","article-title":"Modeling of collision-induced excitation and quenching of atomic nitrogen","volume":"161","year":"2024","journal-title":"J.\u00a0Chem. Phys."},{"issue":"4","key":"2026101407012993900_c24","doi-asserted-by":"publisher","first-page":"046102","DOI":"10.1063\/1.4872336","article-title":"Three-dimensional analytic probabilities of coupled vibrational-rotational-translational energy transfer for DSMC modeling of nonequilibrium flows","volume":"26","year":"2014","journal-title":"Phys. Fluids"},{"issue":"5","key":"2026101407012993900_c25","doi-asserted-by":"publisher","first-page":"1453","DOI":"10.1063\/1.556043","article-title":"Evaluated chemical kinetics data for reactions of N(2D), N(2P), and N2(A3\u03a3u+) in the gas phase","volume":"28","year":"1999","journal-title":"J.\u00a0Phys. Chem. Ref. Data"},{"issue":"11","key":"2026101407012993900_c26","doi-asserted-by":"publisher","first-page":"6170","DOI":"10.1063\/1.450758","article-title":"Nonstatistical effects and detailed balance in quasiclassical trajectory calculations of the thermal rate coefficient for O + OH \u2192 O2 + H","volume":"84","year":"1986","journal-title":"J.\u00a0Chem. Phys."},{"issue":"2","key":"2026101407012993900_c27","doi-asserted-by":"publisher","first-page":"021102","DOI":"10.1063\/1.4734316","article-title":"Communication: Rate coefficients from quasiclassical trajectory calculations from the reverse reaction: The Mu + H2 reaction re-visited","volume":"137","year":"2012","journal-title":"J.\u00a0Chem. Phys."},{"issue":"14","key":"2026101407012993900_c28","doi-asserted-by":"publisher","first-page":"3883","DOI":"10.1021\/j100298a030","article-title":"Rate coefficients for N(2D) reactions","volume":"91","year":"1987","journal-title":"J.\u00a0Phys. Chem."},{"key":"2026101407012993900_c29","doi-asserted-by":"publisher","first-page":"1721","DOI":"10.1039\/f29747001721","article-title":"Kinetic study of electronically excited nitrogen atoms, N(22DJ, 22PJ), by attenuation of atomic resonance radiation in the vacuum ultra-violet","volume":"70","year":"1974","journal-title":"J.\u00a0Chem. Soc., Faraday Trans. 2"},{"issue":"1","key":"2026101407012993900_c30","doi-asserted-by":"publisher","first-page":"116","DOI":"10.1063\/1.1671694","article-title":"Vacuum-ultraviolet photolysis of N2O. IV. Deactivation of N(2D)","volume":"51","year":"1969","journal-title":"J.\u00a0Chem. Phys."},{"issue":"16","key":"2026101407012993900_c31","doi-asserted-by":"publisher","first-page":"2504","DOI":"10.1021\/acs.jpca.6b00480","article-title":"An experimental and theoretical investigation of the C (1D) + N2 \u2192 C(3P) + N2 quenching reaction at low temperature","volume":"120","year":"2016","journal-title":"J.\u00a0Phys. Chem. A"},{"issue":"1510","key":"2026101407012993900_c32","doi-asserted-by":"publisher","first-page":"417","DOI":"10.1098\/rspa.1969.0168","article-title":"Flash photolysis of carbon suboxide: Absolute rate constants for reactions of C(3P) and C (1D) with H2, N2, CO, NO, O2 and CH4","volume":"312","year":"1969","journal-title":"Proc. R. Soc. A"},{"issue":"5","key":"2026101407012993900_c33","doi-asserted-by":"publisher","first-page":"412","DOI":"10.1016\/0009-2614(71)80255-5","article-title":"The study of electronically excited carbon atoms, C(21D2), by photoelectric measurement of time-resolved atomic absorption","volume":"9","year":"1971","journal-title":"Chem. Phys. Lett."},{"issue":"7","key":"2026101407012993900_c34","doi-asserted-by":"publisher","first-page":"3214","DOI":"10.1063\/1.437910","article-title":"A classical analog for electronic degrees of freedom in nonadiabatic collision processes","volume":"70","year":"1979","journal-title":"J.\u00a0Chem. Phys."},{"issue":"32","key":"2026101407012993900_c35","doi-asserted-by":"publisher","first-page":"7190","DOI":"10.1021\/jp401078u","article-title":"Symmetrical windowing for quantum states in quasi-classical trajectory simulations","volume":"117","year":"2013","journal-title":"J.\u00a0Phys. Chem. A"},{"issue":"23","key":"2026101407012993900_c36","doi-asserted-by":"publisher","first-page":"234112","DOI":"10.1063\/1.4845235","article-title":"Symmetrical windowing for quantum states in quasiclassical trajectory simulations: Application to electronically non-adiabatic processes","volume":"139","year":"2013","journal-title":"J.\u00a0Chem. Phys."},{"issue":"14","key":"2026101407012993900_c37","doi-asserted-by":"publisher","first-page":"144108","DOI":"10.1063\/1.4963914","article-title":"A new symmetrical quasi-classical model for electronically non-adiabatic processes: Application to the case of weak non-adiabatic coupling","volume":"145","year":"2016","journal-title":"J.\u00a0Chem. Phys."}],"container-title":["The Journal of Chemical Physics"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.aip.org\/aip\/jcp\/article-pdf\/doi\/10.1063\/5.0358052\/21170407\/144118_1_5.0358052.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.aip.org\/aip\/jcp\/article-pdf\/doi\/10.1063\/5.0358052\/21170407\/144118_1_5.0358052.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T11:01:32Z","timestamp":1791975692000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.aip.org\/jcp\/article\/165\/14\/144118\/3406505\/Semiclassical-model-of-nonadiabatic-energy"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,10,14]]},"references-count":37,"journal-issue":{"issue":"14","published-print":{"date-parts":[[2026,10,14]]}},"URL":"https:\/\/doi.org\/10.1063\/5.0358052","relation":{},"ISSN":["0021-9606","1089-7690"],"issn-type":[{"value":"0021-9606","type":"print"},{"value":"1089-7690","type":"electronic"}],"subject":[],"published-other":{"date-parts":[[2026,10,14]]},"published":{"date-parts":[[2026,10,14]]},"article-number":"144118"}}