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Here, we report the first full-dimensional (12D) time-dependent wave packet study of this reaction on an accurate potential energy surface. Our calculations reveal a striking hierarchy of mode-specific efficacy: excitation of the reacting CH2 stretching modes enhances reactivity by factors of 8.7 and 7.6, while vibrational energy deposited into the spectator CD2 modes proves less effective than translational energy. The torsional and rocking motions exhibit moderate promotional effects. At combustion-relevant temperatures, CH2 stretching excitations collectively contribute over 53% of the thermal rate constant at 2000 K. This work establishes the first rigorous quantum mechanical baseline for mode-selective chemistry in an asymmetric methane isotopologue and provides a powerful framework for elucidating bond-specific dynamics in complex polyatomic systems.<\/jats:p>","DOI":"10.1021\/acs.jpca.6c05608","type":"journal-article","created":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T11:01:34Z","timestamp":1791284494000},"page":"8120-8127","source":"Crossref","is-referenced-by-count":0,"title":["Full-Dimensional Quantum Dynamics of the H + CH2D2 \u2192 H2 + CHD2 Reaction:\nMode-Specific Chemistry in an Asymmetric Methane Isotopologue"],"prefix":"10.1021","volume":"130","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4263-1789","authenticated-orcid":true,"given":"Zhaojun","family":"Zhang","sequence":"first","affiliation":[{"name":"Chinese Academy of Sciences , , ,","place":["Dalian, China, 116023"]},{"name":"University of Chinese Academy of Sciences , ,","place":["Beijing, China, 101408"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9426-8822","authenticated-orcid":true,"given":"Dong H.","family":"Zhang","sequence":"additional","affiliation":[{"name":"Chinese Academy of Sciences , , ,","place":["Dalian, China, 116023"]},{"name":"Hefei National Laboratory , ,","place":["Hefei, China, 230088"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,10,6]]},"reference":[{"key":"2026101508072796800_cit1","doi-asserted-by":"publisher","first-page":"2237","DOI":"10.1063\/1.470920","article-title":"Reduced dimensionality\ncalculations of quantum reactive scattering for the H+CH4 \u2192 H2+CH3 reaction","volume":"104","author":"Takayanagi","year":"1996","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit2","doi-asserted-by":"publisher","first-page":"3508","DOI":"10.1063\/1.479634","article-title":"Four-dimensional quantum scattering calculations on the H + CH4 \u2192 H2 + CH3 reaction","volume":"111","author":"Yu","year":"1999","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit3","doi-asserted-by":"publisher","first-page":"1802","DOI":"10.1063\/1.482013","article-title":"Application of semirigid\nvibrating rotor target model to reaction of H+CH4 \u2192\nCH3+H2","volume":"113","author":"Wang","year":"2000","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit4","doi-asserted-by":"publisher","first-page":"2055","DOI":"10.1063\/1.1383048","article-title":"A reduced dimensionality,\nsix-degree-of-freedom, quantum\ncalculation of the H+CH4 \u2192 H2 + CH3 reaction","volume":"115","author":"Wang","year":"2001","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit5","doi-asserted-by":"publisher","first-page":"1859","DOI":"10.1063\/1.480749","article-title":"A quantum model\nHamiltonian to treat reactions of the\ntype X+YCZ3 \u2192 XY + CZ3: Application to\nO(3P)+CH4 \u2192 OH+CH3","volume":"112","author":"Palma","year":"2000","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit6","doi-asserted-by":"publisher","first-page":"9539","DOI":"10.1063\/1.1524181","article-title":"A seven-dimensional quantum study\nof the H+CH4 reaction","volume":"117","author":"Yang","year":"2002","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit7","doi-asserted-by":"publisher","DOI":"10.1063\/1.2812553","article-title":"A transition state wave packet study\nof the H+CH4 reaction","volume":"127","author":"Zhang","year":"2007","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit8","doi-asserted-by":"publisher","DOI":"10.1063\/1.2434171","article-title":"Seven-dimensional quantum dynamics\nstudy of the O(3P)+CH4 reaction","volume":"126","author":"Yang","year":"2007","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit9","doi-asserted-by":"publisher","first-page":"12782","DOI":"10.1073\/pnas.1006910107","article-title":"Depression of reactivity\nby the collision energy in the single barrier H+CD4 \u2192\nHD+CD3 reaction","volume":"107","author":"Zhang","year":"2010","journal-title":"Proc. Natl. Acad.\nSci. U.S.A."},{"key":"2026101508072796800_cit10","doi-asserted-by":"publisher","first-page":"3416","DOI":"10.1021\/jz301649w","article-title":"Theoretical\nstudy of the validity of the polanyi rules for the late-barrier Cl+CHD3 reaction","volume":"3","author":"Zhang","year":"2012","journal-title":"J. Phys. Chem. 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Phys."},{"key":"2026101508072796800_cit14","doi-asserted-by":"publisher","DOI":"10.1063\/1.4897308","article-title":"Effects of reagent\nrotational excitation on the H +\nCHD3 \u2192 H2 + CD3 reaction:\nA seven dimensional time-dependent wave packet study","volume":"141","author":"Zhang","year":"2014","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit15","doi-asserted-by":"publisher","DOI":"10.1063\/1.4931833","article-title":"An eight-dimensional\nquantum dynamics study of the Cl + CH4 \u2192 HCl + CH3 reaction","volume":"143","author":"Liu","year":"2015","journal-title":"J.\nChem. Phys."},{"key":"2026101508072796800_cit16","doi-asserted-by":"publisher","DOI":"10.1038\/ncomms14506","article-title":"Dynamical barrier\nand isotope effects in the simplest substitution reaction via Walden\ninversion mechanism","volume":"8","author":"Zhao","year":"2017","journal-title":"Nat. Commun."},{"key":"2026101508072796800_cit17","doi-asserted-by":"publisher","first-page":"9202","DOI":"10.1073\/pnas.1917618117","article-title":"Reactivity\noscillation in the heavy-light-heavy Cl+CH4 reaction","volume":"117","author":"Chen","year":"2020","journal-title":"Proc. Natl. Acad. Sci. U.S.A."},{"key":"2026101508072796800_cit18","doi-asserted-by":"publisher","first-page":"7973","DOI":"10.1039\/D3SC02629A","article-title":"Feshbach resonances\nin the F + CHD3 \u2192 HF + CD3 reaction","volume":"14","author":"Liu","year":"2023","journal-title":"Chem. Sci."},{"key":"2026101508072796800_cit19","doi-asserted-by":"publisher","first-page":"1032","DOI":"10.1021\/acs.jpca.3c07348","article-title":"Isotope Effect and\nHeavy-Light-Heavy Reactivity Oscillation in the Cl + CHD3\/CHT3 Reaction","volume":"128","author":"Liu","year":"2024","journal-title":"J. Phys. Chem. 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Phys."},{"key":"2026101508072796800_cit26","doi-asserted-by":"publisher","first-page":"9617","DOI":"10.1021\/jp911880u","article-title":"Full-dimensional\nquantum reaction\nrate calculations for H + CH4 \u2192 H2 +\nCH3 on a recent potential energy surface","volume":"114","author":"Schiffel","year":"2010","journal-title":"J. Phys. Chem. A"},{"key":"2026101508072796800_cit27","doi-asserted-by":"publisher","DOI":"10.1063\/1.4891917","article-title":"Communication: Ro-vibrational control of chemical reactivity\nin H + CH4 \u2192 H2 + CH3: Full-dimensional\nquantum dynamics calculations and a sudden model","volume":"141","author":"Welsch","year":"2014","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit28","doi-asserted-by":"publisher","first-page":"338","DOI":"10.1021\/jz502525p","article-title":"Loss of memory in H+CH4 \u2192 H2+CH3 state-to-state reactive\nscattering","volume":"6","author":"Welsch","year":"2015","journal-title":"J. Phys. Chem. Lett."},{"key":"2026101508072796800_cit29","doi-asserted-by":"publisher","DOI":"10.1063\/1.5018254","article-title":"Communication: Reactivity\nborrowing in the mode selective\nchemistry of H + CHD3 \u2192 H2+CD3","volume":"147","author":"Ellerbrock","year":"2017","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit30","doi-asserted-by":"publisher","first-page":"106","DOI":"10.1016\/j.chemphys.2016.08.032","article-title":"H+CH4 \u2192 H2+CH3 initial state-selected reaction probabilities on different potential\nenergy surfaces","volume":"482","author":"Ellerbrock","year":"2017","journal-title":"Chem. Phys."},{"key":"2026101508072796800_cit31","doi-asserted-by":"publisher","DOI":"10.1063\/1.5037797","article-title":"Full-dimensional quantum\ndynamics calculations for\nH+CHD3 \u2192 H2 + CD3: The effect\nof multiple vibrational excitations","volume":"148","author":"Ellerbrock","year":"2018","journal-title":"J. Chem.\nPhys."},{"key":"2026101508072796800_cit32","doi-asserted-by":"publisher","first-page":"217","DOI":"10.1039\/C8FD00081F","article-title":"Natural reaction channels in H + CHD3 \u2192\nH2 + CD3","volume":"212","author":"Ellerbrock","year":"2018","journal-title":"Faraday Discuss."},{"key":"2026101508072796800_cit33","doi-asserted-by":"publisher","DOI":"10.1126\/sciadv.abm9820","article-title":"Vibrational control of the reaction\npathway in the H + CHD3 \u2192 H2+CD3 reaction","volume":"8","author":"Ellerbrock","year":"2022","journal-title":"Sci. Adv."},{"key":"2026101508072796800_cit34","doi-asserted-by":"publisher","DOI":"10.1063\/5.0076216","article-title":"Initial state-selected scattering\nfor the reactions H + CH4\/CHD3 and F + CHD3 employing ring polymer molecular dynamics","volume":"156","author":"Marjollet","year":"2022","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit35","doi-asserted-by":"publisher","DOI":"10.1063\/5.0033851","article-title":"A ten-dimensional quantum\ndynamics model for the X+YCAB2 reaction: Application to H+CH4 reaction","volume":"153","author":"Liu","year":"2020","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit36","doi-asserted-by":"publisher","DOI":"10.1063\/1.5096047","article-title":"Full dimensional\nquantum mechanical\ncalculations of the reaction probability of the H+NH3 collision\nbased on a mixed Jacobi and Radau description","volume":"150","author":"Zhang","year":"2019","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit37","doi-asserted-by":"publisher","DOI":"10.1063\/5.0009721","article-title":"Full-dimensional\nquantum mechanical\ncalculations of the reaction probability of the H+CH4 reaction\nbased on a mixed Jacobi and Radau description","volume":"152","author":"Zhang","year":"2020","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit38","doi-asserted-by":"publisher","first-page":"1146","DOI":"10.1063\/1.467808","article-title":"Full-dimensional\ntime-dependent treatment for diatom-diatom\nreactions: The H2+OH reaction","volume":"101","author":"Zhang","year":"1994","journal-title":"J.\nChem. Phys."},{"key":"2026101508072796800_cit39","doi-asserted-by":"publisher","first-page":"4544","DOI":"10.1063\/1.471203","article-title":"A six dimensional\nquantum study for atom triatom reactions:\nThe H+H2O \u2192 H2+OH reaction","volume":"104","author":"Zhang","year":"1996","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit40","doi-asserted-by":"publisher","DOI":"10.1063\/1.2967854","article-title":"Full dimensional\ntime-dependent quantum dynamics study of the H+NH3 \u2192\nH2+NH2 reaction","volume":"129","author":"Yang","year":"2008","journal-title":"J. Chem.\nPhys."},{"key":"2026101508072796800_cit41","doi-asserted-by":"publisher","first-page":"2782","DOI":"10.1021\/acs.jctc.6c00050","article-title":"Quantum Dynamics Description of Reactions\nwith Seven Atoms: Application to the OH + CHD3","volume":"22","author":"Zhang","year":"2026","journal-title":"J. Chem. Theory Comput."},{"key":"2026101508072796800_cit42","doi-asserted-by":"publisher","first-page":"181","DOI":"10.1016\/S0166-1280(97)00240-6","article-title":"Vector parametrization\nof the three-atom\nproblem in quantum mechanics","volume":"424","author":"Gatti","year":"1998","journal-title":"J. Mol. Struct.:\nTHEOCHEM"},{"key":"2026101508072796800_cit43","doi-asserted-by":"publisher","first-page":"8821","DOI":"10.1063\/1.476328","article-title":"Vector parametrization\nof the N-atom problem in quantum mechanics. II. Coupled-angular-momentum\nspectral representations for four-atom systems","volume":"108","author":"Gatti","year":"1998","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit44","doi-asserted-by":"publisher","first-page":"8804","DOI":"10.1063\/1.476327","article-title":"Vector parametrization\nof the N-atom problem in quantum\nmechanics. I. Jacobi vectors","volume":"108","author":"Gatti","year":"1998","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit45","doi-asserted-by":"publisher","first-page":"7225","DOI":"10.1063\/1.480051","article-title":"Vector parametrization\nof the N-atom problem in quantum mechanics. III. Separation into two\nsubsystems: Application to NH3","volume":"111","author":"Gatti","year":"1999","journal-title":"J.\nChem. Phys."},{"key":"2026101508072796800_cit46","doi-asserted-by":"publisher","first-page":"1","DOI":"10.1016\/j.physrep.2009.05.003","article-title":"Exact and constrained\nkinetic energy operators for polyatomic molecules:\nThe polyspherical approach","volume":"484","author":"Gatti","year":"2009","journal-title":"Phys. Rep."},{"key":"2026101508072796800_cit47","doi-asserted-by":"publisher","DOI":"10.1063\/1.4950028","article-title":"Full-dimensional vibrational\ncalculations of five-atom molecules\nusing a combination of Radau and Jacobi coordinates: Applications\nto methane and fluoromethane","volume":"144","author":"Zhao","year":"2016","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit48","doi-asserted-by":"publisher","DOI":"10.1063\/1.4921412","article-title":"A permutationally invariant full-dimensional ab initio potential\nenergy surface for the abstraction and exchange channels of the H+CH4 system","volume":"142","author":"Li","year":"2015","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit49","doi-asserted-by":"publisher","DOI":"10.1063\/1.5019323","article-title":"Computing energy levels of CH4, CHD3, CH3D, and CH3F with\na direct product basis and coordinates based on the methyl subsystem","volume":"148","author":"Zhao","year":"2018","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit50","doi-asserted-by":"publisher","first-page":"10067","DOI":"10.1063\/1.1519009","article-title":"Accuracy\nof the centrifugal sudden\napproximation in the H+H2O reaction and accurate integral\ncross sections for the H+H2O \u2192 H2+OH\nabstraction reaction","volume":"117","author":"Zhang","year":"2002","journal-title":"J. Chem. Phys."},{"key":"2026101508072796800_cit51","doi-asserted-by":"publisher","first-page":"2218","DOI":"10.1021\/jp809839t","article-title":"High-Resolution Near Infrared Spectroscopy\nand Vibrational Dynamics of Dideuteromethane (CH2D2)\u2020","volume":"113","author":"Ulenikov","year":"2009","journal-title":"J. Phys. Chem.\nA"}],"container-title":["The Journal of Physical Chemistry A"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.jpca.6c05608","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jpcafh\/article-pdf\/130\/41\/8120\/68753116\/acs.jpca.6c05608.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jpcafh\/article-pdf\/130\/41\/8120\/68753116\/acs.jpca.6c05608.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,15]],"date-time":"2026-10-15T12:30:11Z","timestamp":1792067411000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jpcafh\/article\/130\/41\/8120\/5445001\/Full-Dimensional-Quantum-Dynamics-of-the-H-CH2D2"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,10,6]]},"references-count":51,"journal-issue":{"issue":"41","published-online":{"date-parts":[[2026,10,6]]},"published-print":{"date-parts":[[2026,10,15]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.jpca.6c05608","relation":{},"ISSN":["1089-5639","1520-5215"],"issn-type":[{"value":"1089-5639","type":"print"},{"value":"1520-5215","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,10,6]]}}}