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It is found that the relative importance of electrostatic and orbital (charge transfer) interactions varies as a function of both the donor and acceptor molecules. Hard and soft interactions were distinguished and characterised by atomic charges, electrophilicity and local softness indices. Dual\u2010descriptor plots indicate an orbital \u03c3 hole on the halogen similar to the electrostatic \u03c3 hole manifested in the molecular electrostatic potential. The predicted high halogen\u2010bond\u2010acceptor affinity of N\u2010heterocyclic carbenes was evidenced in the highest complexation energy for the hitherto unknown CF<jats:sub>3<\/jats:sub>I\u22c5NHC complex. The dominant NOCV orbital represents an electron\u2010density deformation according to a n\u2192\u03c3*\u2010type interaction. The characteristic signal found in the reduced density gradient versus electron\u2010density diagram corresponds to the non\u2010covalent interaction between contact atoms in the NCI plots, which is the manifestation of halogen bonding within the NCI theory. The unexpected C\uf8ffX bond strengthening observed in several cases was rationalised within the molecular orbital framework.<\/jats:p>","DOI":"10.1002\/chem.201202567","type":"journal-article","created":{"date-parts":[[2012,11,21]],"date-time":"2012-11-21T02:41:22Z","timestamp":1353465682000},"page":"519-530","source":"Crossref","is-referenced-by-count":120,"title":["Halogen Bonding from a Hard and Soft Acids and Bases Perspective: Investigation by Using Density Functional Theory Reactivity Indices"],"prefix":"10.1002","volume":"19","author":[{"given":"Balazs","family":"Pinter","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nick","family":"Nagels","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wouter A.","family":"Herrebout","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Frank","family":"De\u2005Proft","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2012,11,21]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200800128"},{"key":"e_1_2_6_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200800128"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1168679"},{"key":"e_1_2_6_4_2","unstructured":"\u00a0"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja2105027"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ci900316e"},{"key":"e_1_2_6_7_2","unstructured":"\u00a0"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1039\/b926326h"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201006781"},{"key":"e_1_2_6_9_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201006781"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar0400995"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-540-74330-9"},{"key":"e_1_2_6_12_2","unstructured":"\u00a0"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200906488"},{"key":"e_1_2_6_13_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200906488"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo300279m"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.chemphys.2010.12.012"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.chemphys.2010.06.004"},{"key":"e_1_2_6_17_2","unstructured":"\u00a0"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1002\/cphc.200900125"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1039\/C1CP22771H"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1039\/c0cp02960b"},{"key":"e_1_2_6_21_2","unstructured":"\u00a0"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1039\/c1cp21854a"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201102544"},{"key":"e_1_2_6_23_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201102544"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201101071"},{"key":"e_1_2_6_25_2","unstructured":"\u00a0"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/wcms.19"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1039\/c004189k"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1071\/CH10259"},{"key":"e_1_2_6_29_2","volume":"238","author":"Politzer P.","year":"2009","journal-title":"Abstr. 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