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An Energy Decomposition Analysis in combination with Natural Orbital for Chemical Valence (EDA\u2010NOCV) within the relativistic four\u2010component Dirac\u2010Kohn\u2010Sham (DKS) framework is employed, which allows to successfully include the spin\u2010orbit coupling (SOC) effects on the chemical bond description. Simple halogen\u2010bonded adducts ClX\u22efL (X=At, Ts; L=NH<jats:sub>3<\/jats:sub>, Br<jats:sup>\u2212<\/jats:sup>, H<jats:sub>2<\/jats:sub>O, CO) of astatine and tennessine have been selected to assess a trend on descending along a group, while modulating the ClX\u22efL bond features through the different electronic nature of the ligand L. Interesting effects caused by SOC have been revealed: i) a huge increase of the ClTs dipole moment (which is almost twice as that of ClAt), ii) a lowering of the ClX\u22efL bonding energy arising from different contributions to the ClX\u2026L interaction energy strongly depending on the nature of L, iii) a quenching of one of the <jats:italic>\u03c0<\/jats:italic> back\u2010donation components to the bond. In the ClTs(CO) adduct, the back\u2010donation from ClTs to CO becomes the most important component. The analysis of the electronic structure of the ClX dimers allows for a clear interpretation of the SOC effects in these systems.<\/jats:p>","DOI":"10.1002\/cphc.202400310","type":"journal-article","created":{"date-parts":[[2024,5,6]],"date-time":"2024-05-06T04:53:35Z","timestamp":1714971215000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["The Chemical Bond at the Bottom of the Periodic Table: The Case of the Heavy Astatine and the Super\u2010Heavy Tennessine"],"prefix":"10.1002","volume":"25","author":[{"given":"Giulia","family":"Gamboni","sequence":"first","affiliation":[{"name":"Department of Chemistry Biology and Biotechnology University of Perugia  via Elce di Sotto 8 06123 Perugia Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2888-4990","authenticated-orcid":false,"given":"Leonardo","family":"Belpassi","sequence":"additional","affiliation":[{"name":"CNR Institute of Chemical Science and Technologies \u201cGiulio Natta\u201d (CNR-SCITEC)  via Elce di Sotto 8 06123 Perugia Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1286-9294","authenticated-orcid":false,"given":"Paola","family":"Belanzoni","sequence":"additional","affiliation":[{"name":"Department of Chemistry Biology and Biotechnology University of Perugia  via Elce di Sotto 8 06123 Perugia Italy"},{"name":"CNR Institute of Chemical Science and Technologies \u201cGiulio Natta\u201d (CNR-SCITEC)  via Elce di Sotto 8 06123 Perugia Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2024,6,20]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527664696.ch11"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.8b00722"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1063\/5.0148500"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/qua.560100211"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1007\/BF02401406"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1007\/s00894-006-0149-4"},{"key":"e_1_2_8_7_1","first-page":"962","volume":"4","author":"Mariusz T. 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