{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,12,29]],"date-time":"2025-12-29T22:13:30Z","timestamp":1767046410904,"version":"3.40.5"},"reference-count":37,"publisher":"Wiley","issue":"24","license":[{"start":{"date-parts":[[2024,5,14]],"date-time":"2024-05-14T00:00:00Z","timestamp":1715644800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22373061","21973057"],"award-info":[{"award-number":["22373061","21973057"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100013314","name":"Higher Education Discipline Innovation Project","doi-asserted-by":"publisher","award":["D18001"],"award-info":[{"award-number":["D18001"]}],"id":[{"id":"10.13039\/501100013314","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["J Comput Chem"],"published-print":{"date-parts":[[2024,9,15]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>We show herein that 1,10\u2010dicyano substitution restricts the paragon fluxionality of bullvalene to just 14 isomers which isomerize along a single cycle. The restricted fluxionality of 1,10\u2010dicyanobullvalene (DCB) is investigated by means of: (i) Bonding analyses of the isomer structures using the adaptive natural density partitioning (AdNDP). (ii) Quantum dynamical simulations of the isomerizations along the cyclic intrinsic reaction coordinate of the potential energy surface (PES). The PES possesses 14 equivalent potential wells supporting 14 isomers which are separated by 14 equivalent potential barriers supporting 14 transition states. Accordingly, at low temperatures, DCB appears as a hindered molecular rotor, without any delocalization of the wavefunction in the 14 potential wells, without any nuclear spin isomers, and with completely negligible tunneling. These results are compared and found to differ from those for molecular boron rotors. (iii) Born\u2010Oppenheimer molecular dynamics (BOMD) simulations of thermally activated isomerizations. (iv) Calculations of the rate constants in the frame of transition state theory (TST) with reasonable agreement achieved with the BOMD results. (v) Simulations of the equilibration dynamics using rate equations for the isomerizations with TST rate coefficients. Accordingly, in the long\u2010time limit, isomerizations of the 14 isomers, each with C<jats:sub><jats:italic>s<\/jats:italic><\/jats:sub> symmetry, approach the \u201c14 C<jats:sub><jats:italic>s<\/jats:italic><\/jats:sub>\u2009\u2192\u2009C<jats:sub>7<jats:italic>v<\/jats:italic><\/jats:sub>\u201d thermally averaged structure. This is a superposition of the 14 equally populated isomer structures with an overall C<jats:sub>7<jats:italic>v<\/jats:italic><\/jats:sub> symmetry. By extrapolation, the results for DCB yield working hypotheses for so far un\u2010explored properties e.g. for the equilibration dynamics of C<jats:sub>10<\/jats:sub>H<jats:sub>10<\/jats:sub>.<\/jats:p>","DOI":"10.1002\/jcc.27379","type":"journal-article","created":{"date-parts":[[2024,5,14]],"date-time":"2024-05-14T09:01:28Z","timestamp":1715677288000},"page":"2080-2090","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Restriction on molecular fluxionality by substitution: A case study for the 1,10\u2010dicyanobullvalene"],"prefix":"10.1002","volume":"45","author":[{"given":"Bin\u2010Bin","family":"Pei","sequence":"first","affiliation":[{"name":"Nanocluster Laboratory, Institute of Molecular Science Shanxi University  Taiyuan China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Hongjuan","family":"Yang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Quantum Optics and Quantum Optics Devices, Institute of Laser Spectroscopy Shanxi University  Taiyuan China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Cai\u2010Yue","family":"Gao","sequence":"additional","affiliation":[{"name":"Nanocluster Laboratory, Institute of Molecular Science Shanxi University  Taiyuan China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yuan","family":"Man","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Quantum Optics and Quantum Optics Devices, Institute of Laser Spectroscopy Shanxi University  Taiyuan China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yonggang","family":"Yang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Quantum Optics and Quantum Optics Devices, Institute of Laser Spectroscopy Shanxi University  Taiyuan China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5666-0591","authenticated-orcid":false,"given":"Si\u2010Dian","family":"Li","sequence":"additional","affiliation":[{"name":"Nanocluster Laboratory, Institute of Molecular Science Shanxi University  Taiyuan China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2024,5,14]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(01)99207-5"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19640971125"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/cber.19640971126"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/hlca.19740570518"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/ed078p924"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6NR09074E"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.25728"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.25782"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41598-019-53488-5"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1080\/00268976.2018.1473651"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.5048358"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1CP02980K"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0RA08821H"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00953a045"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00816a037"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00057a038"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.19960020416"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja020741v"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo048268m"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/ol100879t"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp110365g"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201104465"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CP03982G"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.5b11295"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.478522"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.438955"},{"key":"e_1_2_8_28_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.443164"},{"volume-title":"Revision A.03","year":"2016","author":"Frisch M. 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