{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,18]],"date-time":"2026-09-18T18:04:42Z","timestamp":1789754682300,"version":"4.0.1"},"reference-count":51,"publisher":"Wiley","issue":"11","license":[{"start":{"date-parts":[[2023,3,13]],"date-time":"2023-03-13T00:00:00Z","timestamp":1678665600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc\/4.0\/"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPhysChem"],"published-print":{"date-parts":[[2023,6]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    It is shown that repulsive interactions have a crucial influence on the structure of prototypical non\u2010covalently bonded systems. To explain this, we propose a molecular orbital\u2010based model for the exchange\u2010repulsion contribution to the total interaction energy. As a central result, our model shows that energetically preferred aggregate structures frequently exhibit reduced exchange repulsion, which can be deduced from the nodal structure of certain occupied orbitals. This is used to explain key features of the intermolecular potentials of the Cl\n                    <jats:sub>2<\/jats:sub>\n                    \u2010He, benzene\u2010benzene, and benzene\u2010hexafluorobenzene aggregates, which are not correctly reproduced by commonly applied electrostatic models.\n                  <\/jats:p>","DOI":"10.1002\/cphc.202300097","type":"journal-article","created":{"date-parts":[[2023,2,15]],"date-time":"2023-02-15T05:44:02Z","timestamp":1676439842000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":17,"title":["Rationalizing Aggregate Structures with Orbital Contributions to the Exchange\u2010Repulsion Energy**"],"prefix":"10.1002","volume":"24","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5606-8328","authenticated-orcid":false,"given":"Johannes","family":"Henrichsmeyer","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Physikalische und Theoretische Chemie Auf der Morgenstelle 18 Universit\u00e4t T\u00fcbingen  D-72076 T\u00fcbingen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7150-0182","authenticated-orcid":false,"given":"Michael","family":"Thelen","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Physikalische und Theoretische Chemie Auf der Morgenstelle 18 Universit\u00e4t T\u00fcbingen  D-72076 T\u00fcbingen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7238-1584","authenticated-orcid":false,"given":"Marc","family":"Br\u00f6ckel","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Physikalische und Theoretische Chemie Auf der Morgenstelle 18 Universit\u00e4t T\u00fcbingen  D-72076 T\u00fcbingen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8441-9623","authenticated-orcid":false,"given":"Mariam","family":"Fadel","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Physikalische und Theoretische Chemie Auf der Morgenstelle 18 Universit\u00e4t T\u00fcbingen  D-72076 T\u00fcbingen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3797-7272","authenticated-orcid":false,"given":"Stefan","family":"Behnle","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Physikalische und Theoretische Chemie Auf der Morgenstelle 18 Universit\u00e4t T\u00fcbingen  D-72076 T\u00fcbingen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3683-8302","authenticated-orcid":false,"given":"Majda","family":"Sekkal\u2010Rahal","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Physikalische und Theoretische Chemie Auf der Morgenstelle 18 Universit\u00e4t T\u00fcbingen  D-72076 T\u00fcbingen Germany"},{"name":"Departement de Chimie Facult\u00e9 des Sciences Exactes Universit\u00e9 Djillali Liabes de Sidi Bel Abbes  DZ-22000 Sidi Bel Abbes Algeria"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8288-924X","authenticated-orcid":false,"given":"Reinhold F.","family":"Fink","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Physikalische und Theoretische Chemie Auf der Morgenstelle 18 Universit\u00e4t T\u00fcbingen  D-72076 T\u00fcbingen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2023,3,13]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemmater.5b03266"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00188"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar300083h"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200802947"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2sc20045g"},{"key":"e_1_2_8_6_1","doi-asserted-by":"crossref","unstructured":"A. Stone The Theory of Intermolecular Forces Oxford University Press2013.","DOI":"10.1093\/acprof:oso\/9780199672394.001.0001"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar200255p"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp064095o"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp9034375"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4CP03376K"},{"key":"e_1_2_8_11_1","first-page":"439","volume":"72","author":"Reilly A. M.","year":"2016","journal-title":"Acta Crystallogr."},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1098\/rspa.2018.0351"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-021-24119-3"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1080\/01442358609353370"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1039\/c004189k"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00170a016"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr00031a008"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.1c05962"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0SC02667K"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar3001124"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja204294q"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja202932e"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1002\/qua.25513"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja401420w"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jcim.9b00946"},{"key":"e_1_2_8_26_1","author":"Azevedo Santos L.","year":"2023","journal-title":"Chem. Eur. J."},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201702436"},{"key":"e_1_2_8_28_1","unstructured":"The definitions ofEel Edsp Eind andEexrfollow the recommendation of Parkeret al Ref. [34]."},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1002\/qua.560100208"},{"key":"e_1_2_8_30_1","doi-asserted-by":"publisher","DOI":"10.1080\/00268979609482543"},{"key":"e_1_2_8_31_1","unstructured":"The approximate echange-repulsion energyis identical to the SAPT0 value in the asymptotic case of vanishing overlap and for exact Hartree-Fock orbital."},{"key":"e_1_2_8_32_1","unstructured":"J.\u2005C. Slater Quantum Theory of Atomic Structure McGraw-Hill Inc.1960."},{"key":"e_1_2_8_33_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.3159673"},{"key":"e_1_2_8_34_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4867135"},{"key":"e_1_2_8_35_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1579464"},{"key":"e_1_2_8_36_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9CP00300B"},{"key":"e_1_2_8_37_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201812889"},{"key":"e_1_2_8_38_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3cp50892g"},{"key":"e_1_2_8_39_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.23946"},{"key":"e_1_2_8_40_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7CP06959F"},{"key":"e_1_2_8_41_1","doi-asserted-by":"publisher","DOI":"10.1021\/ct050190"},{"key":"e_1_2_8_42_1","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(81)85228-1"},{"key":"e_1_2_8_43_1","doi-asserted-by":"publisher","DOI":"10.1063\/5.0043046"},{"key":"e_1_2_8_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp054461o"},{"key":"e_1_2_8_45_1","doi-asserted-by":"publisher","DOI":"10.1002\/qua.25345"},{"key":"e_1_2_8_46_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CE01187G"},{"key":"e_1_2_8_47_1","unstructured":"The coordinates are chosen according to Mulliken's[51]recommendation for symmetric molecules which setszto theC6axis whiley and xpoint towards an edge and a side of the (hexafluoro)benzene. Consideration of a shift inyor any other direction in the molecular plane does not affect the conclusions below although thexshift results are somewhat more pronounced."},{"key":"e_1_2_8_48_1","doi-asserted-by":"publisher","DOI":"10.1063\/5.0006002"},{"key":"e_1_2_8_49_1","unstructured":"Atx=0\u2005\u00c5overestimates the corresponding SAPT value (Figure\u20052) by about 10\u2009%. However as both curves show the same qualitative behavior it is reliable to analyze the behavior of the exchange-repulsion energy by considering."},{"key":"e_1_2_8_50_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3cp51077h"},{"key":"e_1_2_8_51_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1740655"}],"container-title":["ChemPhysChem"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/cphc.202300097","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/cphc.202300097","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/cphc.202300097","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,14]],"date-time":"2025-10-14T00:46:25Z","timestamp":1760402785000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/cphc.202300097"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,3,13]]},"references-count":51,"journal-issue":{"issue":"11","published-print":{"date-parts":[[2023,6]]}},"alternative-id":["10.1002\/cphc.202300097"],"URL":"https:\/\/doi.org\/10.1002\/cphc.202300097","archive":["Portico"],"relation":{"has-preprint":[{"id-type":"doi","id":"10.26434\/chemrxiv-2022-l60b2","asserted-by":"object"}]},"ISSN":["1439-4235","1439-7641"],"issn-type":[{"value":"1439-4235","type":"print"},{"value":"1439-7641","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,3,13]]},"assertion":[{"value":"2023-02-07","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2023-03-13","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202300097"}}