{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,11]],"date-time":"2026-06-11T14:16:26Z","timestamp":1781187386631,"version":"3.54.1"},"reference-count":134,"publisher":"MDPI AG","issue":"4","license":[{"start":{"date-parts":[[2018,9,20]],"date-time":"2018-09-20T00:00:00Z","timestamp":1537401600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Computation"],"abstract":"<jats:p>The divergence of fluorine-based systems and significance of their nascent non-covalent chemistry in molecular assemblies are presented in a brief review of the field. Emphasis has been placed to show that type-I and -II halogen-centered F\u00b7\u00b7\u00b7F long-ranged intermolecular distances viable between the entirely negative fluorine atoms in some fluoro-substituted dimers of C6H6 can be regarded as the consequence of significant non-covalent attractive interactions. Such attractive interactions observed in the solid-state structures of C6F6 and other similar fluorine-substituted aromatic compounds have frequently been underappreciated. While these are often ascribed to crystal packing effects, we show using first-principles level calculations that these are much more fundamental in nature. The stability and reliability of these interactions are supported by their negative binding energies that emerge from a supermolecular procedure using MP2 (second-order M\u00f8ller-Plesset perturbation theory), and from the Symmetry Adapted Perturbation Theory, in which the latter does not determine the interaction energy by computing the total energy of the monomers or dimer. Quantum Theory of Atoms in Molecules and Reduced Density Gradient Non-Covalent Index charge-density-based approaches confirm the F\u00b7\u00b7\u00b7F contacts are a consequence of attraction by their unified bond path (and bond critical point) and isosurface charge density topologies, respectively. These interactions can be explained neither by the so-called molecular electrostatic surface potential (MESP) model approach that often demonstrates attraction between sites of opposite electrostatic surface potential by means of Coulomb\u2019s law of electrostatics, nor purely by the effect of electrostatic polarization. We provide evidence against the standalone use of this approach and the overlooking of other approaches, as the former does not allow for the calculation of the electrostatic potential on the surfaces of the overlapping atoms on the monomers as in the equilibrium geometry of a complex. This study thus provides unequivocal evidence of the limitation of the MESP approach for its use in gaining insight into the nature of reactivity of overlapped interacting atoms and the intermolecular interactions involved.<\/jats:p>","DOI":"10.3390\/computation6040051","type":"journal-article","created":{"date-parts":[[2018,9,21]],"date-time":"2018-09-21T03:46:35Z","timestamp":1537501595000},"page":"51","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":46,"title":["Can Combined Electrostatic and Polarization Effects Alone Explain the F\u00b7\u00b7\u00b7F Negative-Negative Bonding in Simple Fluoro-Substituted Benzene Derivatives? A First-Principles Perspective"],"prefix":"10.3390","volume":"6","author":[{"given":"Pradeep R.","family":"Varadwaj","sequence":"first","affiliation":[{"name":"Department of Chemical System Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan"},{"name":"National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8568, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Arpita","family":"Varadwaj","sequence":"additional","affiliation":[{"name":"Department of Chemical System Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan"},{"name":"National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8568, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1675-3835","authenticated-orcid":false,"given":"Helder M.","family":"Marques","sequence":"additional","affiliation":[{"name":"Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Johannesburg 2050, South Africa"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Koichi","family":"Yamashita","sequence":"additional","affiliation":[{"name":"Department of Chemical System Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan"},{"name":"National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8568, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2018,9,20]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"685","DOI":"10.1051\/0004-6361:20066934","article-title":"Molecular fluorine chemistry in the early universe","volume":"476","author":"Puy","year":"2007","journal-title":"Astron. Astrophys."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"13","DOI":"10.1039\/C7GC03081A","article-title":"Natural surfactants towards a more sustainable fluorine chemistry","volume":"20","author":"Dichiarante","year":"2018","journal-title":"Green Chem."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"683","DOI":"10.2174\/1389557515666151016124957","article-title":"Application of fluorine in drug design during 2010\u20132015 years: A mini-review","volume":"17","author":"Wang","year":"2017","journal-title":"Mini Rev. Med. Chem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"8315","DOI":"10.1021\/acs.jmedchem.5b00258","article-title":"Applications of fluorine in medicinal chemistry","volume":"58","author":"Gillis","year":"2015","journal-title":"J. Med. Chem."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"399","DOI":"10.1021\/acsinfecdis.6b00036","article-title":"5-fluoroimidazo[4,5-b]pyridine is a privileged fragment that conveys bioavailability to potent trypanosomal methionyl-tRNA synthetase inhibitors","volume":"2","author":"Zhang","year":"2016","journal-title":"ACS Infect. Dis."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"5401","DOI":"10.1021\/jp211177d","article-title":"Fluorine-passivated silicon nanocrystals: Surface chemistry versus quantum confinement","volume":"116","author":"Ma","year":"2012","journal-title":"J. Phys. Chem. C"},{"key":"ref_7","unstructured":"Lowe, D. (2018, July 31). One Does Not Simply Walk into Fluorine Chemistry. Available online: http:\/\/blogs.sciencemag.org\/pipeline\/archives\/2012\/02\/28\/one_does_not_simply_walk_into_fluorine_chemistry."},{"key":"ref_8","first-page":"1000104","article-title":"Importance of fluorine and fluorocarbons in medicinal chemistry and oncology","volume":"1","author":"Menaa","year":"2013","journal-title":"J. Mol. Pharm. Org. Process. Res."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"20381","DOI":"10.1039\/C6CP03862J","article-title":"Electrostatically enhanced F\u22efF interactions through hydrogen bonding, halogen bonding and metal coordination: An ab initio study","volume":"18","author":"Frontera","year":"2016","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"31624","DOI":"10.1039\/C5CP03209A","article-title":"Unusual bonding modes of perfluorobenzene in its polymeric (dimeric, trimeric and tetrameric) forms: Entirely negative fluorine interacting cooperatively with entirely negative fluorine","volume":"17","author":"Varadwaj","year":"2015","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"19098","DOI":"10.1039\/C5RA27039A","article-title":"Can an entirely negative fluorine in a molecule, viz. Perfluorobenzene, interact attractively with the entirely negative site(s) on another molecule(s)? Like liking like!","volume":"6","author":"Varadwaj","year":"2016","journal-title":"RSC Adv."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"7748","DOI":"10.1039\/c004189k","article-title":"Halogen bonding: An electrostatically-driven highly directional noncovalent interaction","volume":"12","author":"Politzer","year":"2010","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"11178","DOI":"10.1039\/c3cp00054k","article-title":"Halogen bonding and other \u03c3-hole interactions: A perspective","volume":"15","author":"Politzer","year":"2013","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"723","DOI":"10.1007\/s00894-008-0386-9","article-title":"Expansion of the \u03c3-hole concept","volume":"15","author":"Murray","year":"2009","journal-title":"J. Mol. Model."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"291","DOI":"10.1007\/s00894-006-0130-2","article-title":"Halogen bonding: The \u03c3-hole","volume":"13","author":"Clark","year":"2007","journal-title":"J. Mol. Model."},{"key":"ref_16","doi-asserted-by":"crossref","unstructured":"Varadwaj, A., Varadwaj, P.R., Marques, H.M., and Yamashita, K. (2018, July 31). Comment on \u201cExtended Halogen Bonding between Fully Fluorinated Aromatic Molecules: Kawai et al., ACS Nano, 2015, 9, 2574, arXiv, Available online: https:\/\/arxiv.org\/ftp\/arxiv\/papers\/1802\/1802.09995.pdf.","DOI":"10.1021\/nn505876n"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"2496","DOI":"10.1002\/cphc.201500314","article-title":"The bright future of unconventional \u03c3\/\u03c0-hole interactions","volume":"16","author":"Mooibroek","year":"2015","journal-title":"ChemPhysChem"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"32166","DOI":"10.1039\/C7CP06793C","article-title":"The s-hole revisited","volume":"19","author":"Politzer","year":"2017","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"2574","DOI":"10.1021\/nn505876n","article-title":"Extended halogen bonding between fully fluorinated aromatic molecules","volume":"9","author":"Kawai","year":"2015","journal-title":"ACS Nano"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"2222","DOI":"10.1002\/chem.200500983","article-title":"Isostructurality, polymorphism and mechanical properties of some hexahalogenated benzenes: The nature of halogen\u22efhalogen interactions","volume":"12","author":"Reddy","year":"2006","journal-title":"Chem. Eur. J."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"12604","DOI":"10.1021\/jp102704q","article-title":"Material- and orientation-dependent reactivity for heterogeneously catalyzed carbon\u2212bromine bond homolysis","volume":"114","author":"Walch","year":"2010","journal-title":"J. Phys. Chem. C"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"1361","DOI":"10.1039\/C6CE02598F","article-title":"Are fluorine-based contacts predictable? A case study in three similar coordination compounds","volume":"19","author":"Khavasi","year":"2017","journal-title":"CrystEngComm"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"117","DOI":"10.1023\/B:STUC.0000011246.24486.63","article-title":"Fluorine\u2013fluorine interactions: NMR and AIM analysis","volume":"15","author":"Alkorta","year":"2004","journal-title":"J. Struct. Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"4139","DOI":"10.1021\/ic0504442","article-title":"Self-assembly of heteroleptic [Cu(dipyrrinato)(hfacac)] complexes directed by fluorine\u2212fluorine interactions","volume":"44","author":"Halper","year":"2005","journal-title":"Inorg. Chem."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"3758","DOI":"10.1039\/c0ce00048e","article-title":"Experimental and theoretical study of uracil derivatives: The crucial role of weak fluorine-fluorine noncovalent interactions","volume":"12","author":"Estarellas","year":"2010","journal-title":"CrystEngComm"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"17","DOI":"10.1007\/s11224-015-0622-8","article-title":"Directionality of intermolecular C\u2013F\u00b7\u00b7\u00b7F\u2013C interactions in crystals: Experimental and theoretical charge density study","volume":"27","author":"Karnoukhova","year":"2016","journal-title":"Struct. Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"12676","DOI":"10.1002\/chem.201500981","article-title":"Creating \u03c3-holes through the formation of beryllium bonds","volume":"21","author":"Brea","year":"2015","journal-title":"Chem. Eur. J."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"1435","DOI":"10.1021\/jp2099976","article-title":"Fluorine\u2013fluorine interactions in the solid state: An experimental and theoretical study","volume":"116","author":"Baker","year":"2012","journal-title":"J. Phys. Chem. A"},{"key":"ref_29","doi-asserted-by":"crossref","unstructured":"Bader, R.F. (1990). Atoms in Molecules: A Quantum Theory, Oxford University Press.","DOI":"10.1093\/oso\/9780198551683.001.0001"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"2175","DOI":"10.1039\/c0ce00538j","article-title":"Role of organic fluorine in crystal engineering","volume":"13","author":"Chopra","year":"2011","journal-title":"CrystEngComm"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"140","DOI":"10.1107\/S2052520616017492","article-title":"Characterization of fluorine-centred \u2018F\u00b7\u00b7\u00b7O\u2019 \u03c3-hole interactions in the solid state","volume":"73","author":"Sirohiwal","year":"2017","journal-title":"Acta Crystallogr. Sec. B"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"7558","DOI":"10.1039\/c3cc43513j","article-title":"Halogen bonding in fluorine: Experimental charge density study on intermolecular F\u22efF and F\u22efS donor-acceptor contacts","volume":"49","author":"Pavan","year":"2013","journal-title":"Chem. Commun."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"1363","DOI":"10.1021\/jm3012068","article-title":"Principles and applications of halogen bonding in medicinal chemistry and chemical biology","volume":"56","author":"Wilcken","year":"2013","journal-title":"J. Med. Chem."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"2781","DOI":"10.1021\/ci400257k","article-title":"Halogen interactions in protein\u2013ligand complexes: Implications of halogen bonding for rational drug design","volume":"53","author":"Sirimulla","year":"2013","journal-title":"J. Chem. Inf. Model."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"453","DOI":"10.1002\/qua.24877","article-title":"Fluorines in tetrafluoromethane as halogen bond donors: Revisiting address the nature of the fluorine\u2019s \u03c3-hole","volume":"115","author":"Varadwaj","year":"2015","journal-title":"Int. J. Quantum Chem."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"343","DOI":"10.1002\/jcc.25125","article-title":"Do surfaces of positive electrostatic potential on different halogen derivatives in molecules attract? Like attracting like!","volume":"39","author":"Varadwaj","year":"2018","journal-title":"J. Comput. Chem."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"1033","DOI":"10.1007\/s00894-007-0225-4","article-title":"\u03a3-hole bonding: Molecules containing group VI atoms","volume":"13","author":"Murray","year":"2007","journal-title":"J. Mol. Model."},{"key":"ref_38","doi-asserted-by":"crossref","unstructured":"Varadwaj, A., Varadwaj, P.R., Marques, H.M., and Yamashita, K. (2018). Revealing factors influencing the fluorine-centered non-covalent interactions in some fluorine-substituted molecular complexes: Insights from first-principles studies. ChemPhysChem.","DOI":"10.1002\/cphc.201800023"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"2564","DOI":"10.1002\/jcc.21836","article-title":"Molecular mechanical study of halogen bonding in drug discovery","volume":"32","author":"Ibrahim","year":"2011","journal-title":"J. Comput. Chem."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"3530","DOI":"10.1021\/jp984726h","article-title":"On the nature of the water\u2212hexafluorobenzene interaction","volume":"103","author":"Danten","year":"1999","journal-title":"J. Phys. Chem. A"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"2027","DOI":"10.1021\/jp054461o","article-title":"Intermolecular interaction between hexafluorobenzene and benzene:\u2009 Ab initio calculations including CCSD(T) level electron correlation correction","volume":"110","author":"Tsuzuki","year":"2006","journal-title":"J. Phys. Chem. A"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"9261","DOI":"10.1021\/jo061235h","article-title":"Substituent effects in C6F6C6H5X stacking interactions","volume":"71","author":"Gung","year":"2006","journal-title":"J. Org. Chem."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"459","DOI":"10.1023\/A:1012276824422","article-title":"A theoretical and experimental study of the interaction of c6f6 with electron donors","volume":"12","author":"Alkorta","year":"2001","journal-title":"Struct. Chem."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"2487","DOI":"10.1002\/cphc.200600343","article-title":"Interplay between cation\u2013\u03c0, anion\u2013\u03c0 and \u03c0\u2013\u03c0 interactions","volume":"7","author":"Frontera","year":"2006","journal-title":"ChemPhysChem"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"4102","DOI":"10.1063\/1.451920","article-title":"A determination of the stabilities and structures of F\u2212(C6H6) and F\u2212 (C6F6) clusters","volume":"86","author":"Hiraoka","year":"1987","journal-title":"J. Chem. Phys."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"1762","DOI":"10.1002\/jcc.24816","article-title":"Four faces of the interaction between ions and aromatic rings","volume":"38","author":"Papp","year":"2017","journal-title":"J. Comput. Chem."},{"key":"ref_47","doi-asserted-by":"crossref","unstructured":"Scheiner, S. (2015). Anion-\u03c0 interactions in supramolecular chemistry and catalysis. Noncovalent Forces. Challenges and Advances in Computational Chemistry and Physics, Springer.","DOI":"10.1007\/978-3-319-14163-3"},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"9961","DOI":"10.3390\/molecules20069961","article-title":"Interplay between beryllium bonds and anion-\u03c0 interactions in BeR2:C6X6:Y\u2212 complexes (R = H, F and Cl, X = H and F, and Y = Cl and Br)","volume":"20","author":"Alkorta","year":"2015","journal-title":"Molecules"},{"key":"ref_49","first-page":"127","article-title":"Anions and p-aromatic systems. Do they interact attractively?","volume":"Volume 129","author":"Vilar","year":"2009","journal-title":"Recognition of Anions. Structure and Bonding"},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"323","DOI":"10.1038\/nchem.1004","article-title":"Dihydrogen contacts in alkanes are subtle but not faint","volume":"3","author":"Danovich","year":"2011","journal-title":"Nat. Chem."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"191","DOI":"10.1289\/ehp.8561191","article-title":"Molecular electrostatic potentials: An effective tool for the elucidation of biochemical phenomena","volume":"61","author":"Politzer","year":"1985","journal-title":"Environ. Health Perspect."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"2675","DOI":"10.1002\/cphc.201700637","article-title":"On atoms-in-molecules energies from kohn-sham calculations","volume":"18","author":"Tognetti","year":"2017","journal-title":"ChemPhysChem"},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"094106","DOI":"10.1063\/1.4867135","article-title":"Levels of symmetry adapted perturbation theory (SAPT). I. Efficiency and performance for interaction energies","volume":"140","author":"Parker","year":"2014","journal-title":"J. Chem. Phys."},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"6498","DOI":"10.1021\/ja100936w","article-title":"Revealing noncovalent interactions","volume":"132","author":"Johnson","year":"2010","journal-title":"J. Am. Chem. Soc."},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"571","DOI":"10.1002\/open.201700052","article-title":"Dispersion interactions and the stability of amine dimers","volume":"6","author":"Guttmann","year":"2017","journal-title":"ChemistryOpen"},{"key":"ref_56","doi-asserted-by":"crossref","first-page":"4760","DOI":"10.1002\/anie.201801531","article-title":"Formation of agostic structures driven by London dispersion","volume":"57","author":"Qing","year":"2018","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_57","doi-asserted-by":"crossref","first-page":"2775","DOI":"10.1080\/00268976.2017.1317861","article-title":"Quasi-relativistic two-component computations of intermolecular dispersion energies","volume":"115","author":"Holzer","year":"2017","journal-title":"Mol. Phys."},{"key":"ref_58","doi-asserted-by":"crossref","first-page":"181101","DOI":"10.1063\/1.5007929","article-title":"Symmetry-adapted perturbation theory with intermolecular induction and dispersion energies from the bethe-salpeter equation","volume":"147","author":"Holzer","year":"2017","journal-title":"J. Chem. Phys."},{"key":"ref_59","doi-asserted-by":"crossref","first-page":"13093","DOI":"10.1039\/C7CP01781B","article-title":"Gas-phase structure of 1,8-bis[(trimethylsilyl)ethynyl]anthracene: Cog-wheel-type vs. Independent internal rotation and influence of dispersion interactions","volume":"19","author":"Otlyotov","year":"2017","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_60","doi-asserted-by":"crossref","first-page":"553","DOI":"10.1080\/00268977000101561","article-title":"The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors","volume":"19","author":"Boys","year":"1970","journal-title":"Mol. Phys."},{"key":"ref_61","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., and Petersson, G.A. (2009). Gaussian 09, Gaussian, Inc.. Revision A 02."},{"key":"ref_62","unstructured":"(2017, November 16). SAPT: Symmetry Adapted Perturbation Theory. Available online: http:\/\/www.psicode.org\/psi4manual\/master\/sapt.html."},{"key":"ref_63","doi-asserted-by":"crossref","first-page":"254","DOI":"10.1002\/wcms.86","article-title":"Symmetry-adapted perturbation theory of intermolecular forces","volume":"2","author":"Krzysztof","year":"2012","journal-title":"Wiley Interdiscip. Rev. Comput. Mol. Sci."},{"key":"ref_64","doi-asserted-by":"crossref","first-page":"1887","DOI":"10.1021\/cr00031a008","article-title":"Perturbation theory approach to intermolecular potential energy surfaces of van der Waals complexes","volume":"94","author":"Jeziorski","year":"1994","journal-title":"Chem. Rev."},{"key":"ref_65","doi-asserted-by":"crossref","first-page":"3185","DOI":"10.1021\/acs.jctc.7b00174","article-title":"Psi4 1.1: An open-source electronic structure program emphasizing automation, advanced libraries, and interoperability","volume":"13","author":"Parrish","year":"2017","journal-title":"J. Chem. Theory Comp."},{"key":"ref_66","unstructured":"Keith, T.A. (Aimall, 2016). Aimall, version 17.01.25."},{"key":"ref_67","doi-asserted-by":"crossref","first-page":"580","DOI":"10.1002\/jcc.22885","article-title":"Multiwfn: A multifunctional wavefunction analyzer","volume":"33","author":"Lu","year":"2012","journal-title":"J. Comp. Chem."},{"key":"ref_68","doi-asserted-by":"crossref","first-page":"1396","DOI":"10.1103\/PhysRevLett.78.1396","article-title":"Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]","volume":"78","author":"Perdew","year":"1997","journal-title":"Phys. Rev. Lett."},{"key":"ref_69","doi-asserted-by":"crossref","first-page":"2495","DOI":"10.1002\/jcc.24475","article-title":"Electrostatic component of binding energy: Interpreting predictions from poisson\u2013boltzmann equation and modeling protocols","volume":"37","author":"Arghya","year":"2016","journal-title":"J. Comp. Chem."},{"key":"ref_70","doi-asserted-by":"crossref","first-page":"152101","DOI":"10.1088\/0953-8984\/25\/15\/152101","article-title":"Electrostatic considerations affecting the calculated homo\u2013lumo gap in protein molecules","volume":"25","author":"Lever","year":"2013","journal-title":"J. Phys. Condens. Matter"},{"key":"ref_71","doi-asserted-by":"crossref","first-page":"1524","DOI":"10.1021\/ct1006983","article-title":"A fast and robust poisson\u2013boltzmann solver based on adaptive cartesian grids","volume":"7","author":"Boschitsch","year":"2011","journal-title":"J. Chem. Theory Comp."},{"key":"ref_72","doi-asserted-by":"crossref","first-page":"273","DOI":"10.1016\/j.jocs.2016.03.010","article-title":"Comparative analysis of electrostatic potential maxima and minima on molecular surfaces, as determined by three methods and a variety of basis sets","volume":"17","author":"Riley","year":"2016","journal-title":"J. Comp. Sci."},{"key":"ref_73","doi-asserted-by":"crossref","unstructured":"Politzer, P., and Murray, J.S. (2017). \u03a3-hole interactions: Perspectives and misconceptions. Crystals, 7.","DOI":"10.3390\/cryst7070212"},{"key":"ref_74","doi-asserted-by":"crossref","first-page":"153","DOI":"10.1002\/wcms.19","article-title":"The electrostatic potential: An overview","volume":"1","author":"Murray","year":"2011","journal-title":"Wiley Interdiscip. Rev. Comput. Mol. Sci."},{"key":"ref_75","doi-asserted-by":"crossref","first-page":"22","DOI":"10.1039\/b206867b","article-title":"Distance criteria for crystal packing analysis of supramolecular motifs","volume":"27","author":"Dance","year":"2003","journal-title":"New J. Chem."},{"key":"ref_76","doi-asserted-by":"crossref","first-page":"7968","DOI":"10.1021\/ja00260a006","article-title":"Properties of atoms in molecules: Atomic volumes","volume":"109","author":"Bader","year":"1987","journal-title":"J. Am. Chem. Soc."},{"key":"ref_77","doi-asserted-by":"crossref","first-page":"19573","DOI":"10.1039\/C4CP02663B","article-title":"Halogen bonding interaction of chloromethane withseveral nitrogen donating molecules: Addressing thenature of the chlorine surface \u03c3-hole","volume":"16","author":"Varadwaj","year":"2014","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_78","doi-asserted-by":"crossref","first-page":"4779","DOI":"10.1021\/ct4005454","article-title":"Atomic charges and the electrostatic potential are ill-defined in degenerate ground states","volume":"9","author":"Bultinck","year":"2013","journal-title":"J. Chem. Theory Comput."},{"key":"ref_79","doi-asserted-by":"crossref","first-page":"11543","DOI":"10.1039\/c3cp50962a","article-title":"Intramolecular halogen\u2013halogen bonds?","volume":"15","author":"Johansson","year":"2013","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_80","doi-asserted-by":"crossref","first-page":"32155","DOI":"10.1039\/C6CP06449C","article-title":"Theoretical study on \u03c3- and \u03c0-hole carbon\u00b7\u00b7\u00b7carbon bonding interactions: Implications in CFC chemistry","volume":"18","author":"Frontera","year":"2016","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_81","doi-asserted-by":"crossref","first-page":"8617","DOI":"10.1039\/c3dt50599e","article-title":"A cartography of the van der waals territories","volume":"42","author":"Alvarez","year":"2013","journal-title":"Dalton Trans."},{"key":"ref_82","doi-asserted-by":"crossref","first-page":"145","DOI":"10.1039\/a809309a","article-title":"The C\u2013H\u00b7\u00b7\u00b7Cl hydrogen bond: Does it exist?","volume":"23","author":"Evans","year":"1999","journal-title":"New J. Chem."},{"key":"ref_83","doi-asserted-by":"crossref","first-page":"1413","DOI":"10.1039\/C7NJ03632A","article-title":"On the \u03c3, \u03c0 and \u03b4 hole interactions: A molecular orbital overview","volume":"42","author":"Angarov","year":"2018","journal-title":"New J. Chem."},{"key":"ref_84","doi-asserted-by":"crossref","first-page":"2713","DOI":"10.1002\/slct.201601840","article-title":"Can fluorine form halogen bond? Investigation of halogen bonds through steric charge","volume":"2","author":"Koohi","year":"2017","journal-title":"ChemistrySelect"},{"key":"ref_85","doi-asserted-by":"crossref","first-page":"27","DOI":"10.1016\/j.cplett.2012.02.063","article-title":"A new class of halogen bonds that avoids the \u03c3-hole","volume":"532","author":"Zhang","year":"2012","journal-title":"Chem. Phys. Lett."},{"key":"ref_86","doi-asserted-by":"crossref","unstructured":"Stenlid, J.H., Johansson, A.J., and Brinck, T. (2017). \u03a3-holes on transition metal nanoclusters and their influence on the local lewis acidity. Crystals, 7.","DOI":"10.3390\/cryst7070222"},{"key":"ref_87","doi-asserted-by":"crossref","first-page":"9","DOI":"10.1016\/j.cplett.2010.04.021","article-title":"Halogen bonding: A lump-hole interaction","volume":"492","author":"Eskandari","year":"2010","journal-title":"Chem. Phys. Lett."},{"key":"ref_88","doi-asserted-by":"crossref","first-page":"2478","DOI":"10.1021\/acs.chemrev.5b00484","article-title":"The halogen bond","volume":"116","author":"Cavallo","year":"2016","journal-title":"Chem. Rev."},{"key":"ref_89","doi-asserted-by":"crossref","first-page":"10350","DOI":"10.1039\/c3cp50892g","article-title":"On the directionality of halogen bonding","volume":"15","author":"Huber","year":"2013","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_90","doi-asserted-by":"crossref","first-page":"090044","DOI":"10.1063\/1.4938852","article-title":"Origin of attraction and directionality of hydrogen bond and halogen bond: Analysis by ab initio MO calculations","volume":"1702","author":"Tsuzuki","year":"2015","journal-title":"AIP Conf. Proc."},{"key":"ref_91","doi-asserted-by":"crossref","first-page":"3746","DOI":"10.1021\/jp511118s","article-title":"Double hole-lump interaction between halogen atoms","volume":"119","author":"Duarte","year":"2015","journal-title":"J. Phys. Chem. A"},{"key":"ref_92","doi-asserted-by":"crossref","first-page":"2829","DOI":"10.1098\/rspa.2012.0133","article-title":"Electrostatics of two charged conducting spheres","volume":"468","author":"Lekner","year":"2012","journal-title":"Proc. Roy. Soc. A"},{"key":"ref_93","doi-asserted-by":"crossref","unstructured":"Ball, P. (2012). Like attracts like? Everything you thought you knew about electrostatics is probably wrong. Nature.","DOI":"10.1038\/nature.2012.10698"},{"key":"ref_94","doi-asserted-by":"crossref","first-page":"3177","DOI":"10.1039\/C4CS00375F","article-title":"Energy decomposition analysis approaches and their evaluation on prototypical protein-drug interaction patterns","volume":"44","author":"Phipps","year":"2015","journal-title":"Chem. Soc. Rev."},{"key":"ref_95","doi-asserted-by":"crossref","first-page":"142","DOI":"10.1007\/s00894-018-3684-x","article-title":"On bond-critical points in qtaim and weak interactions","volume":"24","author":"Wick","year":"2018","journal-title":"J. Mol. Model."},{"key":"ref_96","doi-asserted-by":"crossref","first-page":"523","DOI":"10.1002\/wcms.1189","article-title":"The many faces of halogen bonding: A review of theoretical models and methods","volume":"4","author":"Wolters","year":"2014","journal-title":"Wiley Interdiscip. Rev. Comput. Mol. Sci."},{"key":"ref_97","doi-asserted-by":"crossref","first-page":"12190","DOI":"10.1021\/jacs.7b05461","article-title":"Dispersion and halogen-bonding interactions: Binding of the axial conformers of monohalo- and (\u00b1)-trans-1,2-dihalocyclohexanes in enantiopure alleno-acetylenic cages","volume":"139","author":"Gropp","year":"2017","journal-title":"J. Am. Chem. Soc"},{"key":"ref_98","doi-asserted-by":"crossref","first-page":"9031494","DOI":"10.1155\/2017\/9031494","article-title":"Description of weak halogen bonding using various levels of symmetry-adapted perturbation theory combined with effective core potentials","volume":"2017","author":"Matczak","year":"2017","journal-title":"J. Chem."},{"key":"ref_99","doi-asserted-by":"crossref","first-page":"791","DOI":"10.1039\/C6CP07475H","article-title":"On the role of charge transfer in halogen bonding","volume":"19","year":"2017","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_100","doi-asserted-by":"crossref","unstructured":"Scheiner, S. (2017). Halogen bonds formed between substituted imidazoliums and n bases of varying n-hybridization. Molecules, 22.","DOI":"10.3390\/molecules22101634"},{"key":"ref_101","doi-asserted-by":"crossref","first-page":"094106","DOI":"10.1063\/1.3213194","article-title":"Dispersion-corrected m\u00f8ller\u2013plesset second-order perturbation theory","volume":"131","author":"Tkatchenko","year":"2009","journal-title":"J. Chem. Phys."},{"key":"ref_102","doi-asserted-by":"crossref","first-page":"4357","DOI":"10.1063\/1.457743","article-title":"On decomposition of second-order m\u00f8ller-plesset supermolecular interaction energy and basis set effects","volume":"92","author":"Cybulski","year":"1990","journal-title":"J. Chem. Phys."},{"key":"ref_103","doi-asserted-by":"crossref","first-page":"141102","DOI":"10.1063\/1.2795693","article-title":"The origin of deficiency of the supermolecule second-order moller-plesset approach for evaluating interaction energies","volume":"127","author":"Cybulski","year":"2007","journal-title":"J. Chem. Phys."},{"key":"ref_104","doi-asserted-by":"crossref","first-page":"10391","DOI":"10.1021\/jp906341r","article-title":"Bond paths are not chemical bonds","volume":"113","author":"Bader","year":"2009","journal-title":"J. Phys. Chem. A"},{"key":"ref_105","doi-asserted-by":"crossref","unstructured":"Buralli, G.J., Petelski, A.N., Peruchena, N.M., Sosa, G.L., and Duarte, D.R.J. (2017). Multicenter (FX)n\/NH3 halogen bonds (X = Cl, Br and n = 1\u20135). Qtaim descriptors of the strength of the X\u2219\u2219\u2219N interaction. Molecules, 22.","DOI":"10.3390\/molecules22112034"},{"key":"ref_106","doi-asserted-by":"crossref","first-page":"20986","DOI":"10.1039\/C5CP07021J","article-title":"Extension of the interacting quantum atoms (IQA) approach to B3LYP level density functional theory (DFT)","volume":"18","author":"Maxwell","year":"2016","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_107","doi-asserted-by":"crossref","first-page":"344","DOI":"10.1002\/jcc.20173","article-title":"Two-electron integrations in the quantum theory of atoms in molecules with correlated wave functions","volume":"26","author":"Francisco","year":"2005","journal-title":"J. Comp. Chem."},{"key":"ref_108","doi-asserted-by":"crossref","first-page":"8969","DOI":"10.1021\/jp4059774","article-title":"On the physical nature of halogen bonds: A QTAIM study","volume":"117","author":"Syzgantseva","year":"2013","journal-title":"J. Phys. Chem. A"},{"key":"ref_109","doi-asserted-by":"crossref","first-page":"1439","DOI":"10.1021\/acs.jpca.7b11881","article-title":"Fluorine gauche effect explained by electrostatic polarization instead of hyperconjugation: An interacting quantum atoms (IQA) and relative energy gradient (REG) study","volume":"122","author":"Thacker","year":"2018","journal-title":"J. Phys. Chem. A"},{"key":"ref_110","doi-asserted-by":"crossref","first-page":"5552","DOI":"10.1063\/1.1351878","article-title":"Hydrogen bond cooperativity and electron delocalization in hydrogen fluoride clusters","volume":"114","author":"Almeida","year":"2001","journal-title":"J. Chem. Phys."},{"key":"ref_111","doi-asserted-by":"crossref","first-page":"452","DOI":"10.1021\/jp210940b","article-title":"Electron density characteristics in bond critical point (QTAIM) versus interaction energy components (SAPT): The case of charge-assisted hydrogen bonding","volume":"116","author":"Bankiewicz","year":"2012","journal-title":"J. Phys. Chem. A"},{"key":"ref_112","doi-asserted-by":"crossref","unstructured":"Matta, C.F., and Boyd, R.J.T. (2007). The Quantum Theory of Atoms in Molecules, Wiley-VCH.","DOI":"10.1002\/9783527610709"},{"key":"ref_113","doi-asserted-by":"crossref","first-page":"2640","DOI":"10.1021\/jp8106183","article-title":"Polar covalent bonds: An aim analysis of S,O bonds","volume":"113","author":"Love","year":"2009","journal-title":"J. Phys. Chem. A"},{"key":"ref_114","unstructured":"Bader, R.F.W. (2018, July 31). Atoms in Molecules. Available online: http:\/\/www.wiley.com\/legacy\/wileychi\/ecc\/samples\/sample02.pdf."},{"key":"ref_115","doi-asserted-by":"crossref","first-page":"5401","DOI":"10.1002\/chem.201705163","article-title":"Why bond critical points are not \u201cbond\u201d critical points","volume":"24","author":"Shahbazian","year":"2018","journal-title":"Chem. Eur. J."},{"key":"ref_116","doi-asserted-by":"crossref","first-page":"5155","DOI":"10.1021\/acs.chemrev.5b00560","article-title":"Computer modeling of halogen bonds and other \u03c3-hole interactions","volume":"116","author":"Hobza","year":"2016","journal-title":"Chem. Rev."},{"key":"ref_117","doi-asserted-by":"crossref","first-page":"451","DOI":"10.1071\/CH13531","article-title":"Role of polarization in halogen bonds","volume":"67","author":"Clark","year":"2014","journal-title":"Aust. J. Chem."},{"key":"ref_118","doi-asserted-by":"crossref","first-page":"3263","DOI":"10.1021\/ct400420r","article-title":"Are bond critical points really critical for hydrogen bonding?","volume":"9","author":"Lane","year":"2013","journal-title":"J. Chem. Theory Comput."},{"key":"ref_119","doi-asserted-by":"crossref","first-page":"17096","DOI":"10.1021\/ja055827d","article-title":"Weak intramolecular interactions in ethylene glycol identified by vapor phase OH\u2212stretching overtone spectroscopy","volume":"127","author":"Howard","year":"2005","journal-title":"J. Am. Chem. Soc."},{"key":"ref_120","doi-asserted-by":"crossref","first-page":"10245","DOI":"10.1021\/jp063631+","article-title":"Influence of intramolecular hydrogen bond strength on OH-stretching overtones","volume":"110","author":"Howard","year":"2006","journal-title":"J. Phys. Chem. A"},{"key":"ref_121","doi-asserted-by":"crossref","first-page":"33","DOI":"10.1016\/0263-7855(96)00018-5","article-title":"VMD: Visual molecular dynamics","volume":"14","author":"Humphrey","year":"1996","journal-title":"J. Mol. Graph."},{"key":"ref_122","doi-asserted-by":"crossref","first-page":"3669","DOI":"10.1021\/jp045044z","article-title":"Characterization of a closed-shell fluorine\u2212fluorine bonding interaction in aromatic compounds on the basis of the electron density","volume":"109","author":"Matta","year":"2005","journal-title":"J. Phys. Chem. A"},{"key":"ref_123","doi-asserted-by":"crossref","first-page":"3611","DOI":"10.1021\/acs.cgd.7b00736","article-title":"The mouse in a trap: Observation of a C(sp3)\u2013F\u00b7\u00b7\u00b7F\u2013C(sp3) interaction in a discrete CFC pair by the crystal sponge method","volume":"17","author":"Sanna","year":"2017","journal-title":"Cryst. Growth Des."},{"key":"ref_124","doi-asserted-by":"crossref","first-page":"2371","DOI":"10.1021\/acs.cgd.6b00157","article-title":"Effects of fluorine substitution on the intermolecular interactions, energetics, and packing behavior of N-benzyl substituted diketopyrrolopyrroles","volume":"16","author":"Morris","year":"2016","journal-title":"Cryst. Growth Des."},{"key":"ref_125","doi-asserted-by":"crossref","first-page":"834","DOI":"10.1021\/acs.cgd.6b01673","article-title":"Coordination polymers with intramolecular fluorine-involved contacts in two-dimensional sheet windows","volume":"17","author":"Khavasi","year":"2017","journal-title":"Cryst. Growth Des."},{"key":"ref_126","doi-asserted-by":"crossref","first-page":"11314","DOI":"10.1002\/slct.201702047","article-title":"Fluorine-substituted ligands induce structural diversity of coordination compounds","volume":"2","author":"Khavasi","year":"2017","journal-title":"ChemistrySelect"},{"key":"ref_127","doi-asserted-by":"crossref","first-page":"7209","DOI":"10.1002\/anie.201702950","article-title":"Stabilizing fluorine\u2013\u03c0 interactions","volume":"56","author":"Li","year":"2017","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_128","doi-asserted-by":"crossref","first-page":"741","DOI":"10.1007\/s10947-009-0113-0","article-title":"C-F\u00b7\u00b7\u00b7\u03c0, F\u00b7\u00b7\u00b7H, and F\u00b7\u00b7\u00b7F intermolecular interactions and F-aggregation: Role in crystal engineering of fluoroorganic compounds","volume":"50","author":"Rybalova","year":"2009","journal-title":"J. Struct. Chem."},{"key":"ref_129","doi-asserted-by":"crossref","first-page":"772","DOI":"10.1002\/cphc.201700027","article-title":"Trifluoromethyl: An amphiphilic noncovalent bonding partner","volume":"18","author":"Esterhuysen","year":"2017","journal-title":"ChemPhysChem"},{"key":"ref_130","doi-asserted-by":"crossref","first-page":"7901","DOI":"10.1021\/jp504568c","article-title":"Analysis of CF\u00b7\u00b7\u00b7FC interactions on cyclohexane and naphthalene frameworks","volume":"118","author":"Cormanich","year":"2014","journal-title":"J. Phys. Chem. A"},{"key":"ref_131","unstructured":"Sun, H., Tottempudi, U.K., Mottishaw, J.D., Basa, P.N., Putta, A., and Sykes, A.G. (2018, July 31). CCDC 889164: Experimental Crystal Structure Determination. Available online: https:\/\/www.ccdc.cam.ac.uk\/structures\/search?id=doi:10.5517\/ccyv7qq&sid=DataCite."},{"key":"ref_132","doi-asserted-by":"crossref","first-page":"113","DOI":"10.1039\/C7FD00062F","article-title":"Close contacts and noncovalent interactions in crystals","volume":"203","author":"Murray","year":"2017","journal-title":"Faraday Discuss."},{"key":"ref_133","unstructured":"Kuduva, S.S., and Boese, R. (2018, July 31). CCDC 220154: Experimental Crystal Structure Determination. Available online: https:\/\/www.ccdc.cam.ac.uk\/structures\/search?id=doi:10.5517\/cc7d2rf&sid=DataCite."},{"key":"ref_134","doi-asserted-by":"crossref","first-page":"301","DOI":"10.1016\/S0022-1139(99)00292-4","article-title":"Contributions to bis(perfluoroalkyl) chalkogenide chemistry: Preparation of (Rf)2SeO [Rf = C2F5, (CF3)2CF, n-C4F9], (Rf\u2032)2TeX2 [X = F, Cl: Rf\u2032 = n-C3F7, (CF3)2CF, n-C4F9; X = Br: Rf\u2032 = n-C3F7, n-C4F9], (CF3)2Te(NSO)2 and (C2F5)2Te(OH)NO3","volume":"102","author":"Gockel","year":"2000","journal-title":"J. Fluor. Chem."}],"container-title":["Computation"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2079-3197\/6\/4\/51\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T15:21:38Z","timestamp":1760196098000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2079-3197\/6\/4\/51"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2018,9,20]]},"references-count":134,"journal-issue":{"issue":"4","published-online":{"date-parts":[[2018,12]]}},"alternative-id":["computation6040051"],"URL":"https:\/\/doi.org\/10.3390\/computation6040051","relation":{},"ISSN":["2079-3197"],"issn-type":[{"value":"2079-3197","type":"electronic"}],"subject":[],"published":{"date-parts":[[2018,9,20]]}}}