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Here, we present the first computational study of these \u03c0\u2010dimers in solution, with explicit consideration of solvent molecules and finite temperature effects. By means of force\u2010field and ab initio molecular dynamics and free energy simulations, the structure and stability of \u03c0\u2010[TCNE]<jats:sub>2<\/jats:sub><jats:sup>2\u2212<\/jats:sup> (TCNE=tetracyanoethylene) dimers in dichloromethane have been evaluated. Although the dimers dissociate at room temperature, they are stable at 175\u2005K and their structure is similar to the one in the solid state, with a cofacial arrangement of the radicals at an interplanar separation of approximately 3.0\u2005\u00c5. The \u03c0\u2010[TCNE]<jats:sub>2<\/jats:sub><jats:sup>2\u2212<\/jats:sup> dimers form dissociated ion pairs with the NBu<jats:sub>4<\/jats:sub><jats:sup>+<\/jats:sup> counterions, and their first solvation shell comprises approximately 20 CH<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub> molecules. Among them, the eight molecules distributed along the equatorial plane of the dimer play a key role in stabilizing the dimer through bridging C\u2212H\u22c5\u22c5\u22c5N contacts. The calculated free energy of dimerization of TCNE<jats:bold><jats:sup>.<\/jats:sup><\/jats:bold><jats:sup>\u2212<\/jats:sup> in solution at 175\u2005K is \u22125.5\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>. These results provide the first quantitative model describing the pairing of radical ions in solution, and demonstrate the key role of solvation forces on the dimerization process.<\/jats:p>","DOI":"10.1002\/chem.201603537","type":"journal-article","created":{"date-parts":[[2016,10,13]],"date-time":"2016-10-13T11:59:15Z","timestamp":1476359955000},"page":"17037-17046","source":"Crossref","is-referenced-by-count":7,"title":["Formation of Long, Multicenter \u03c0\u2010[TCNE]<sub>2<\/sub><sup>2\u2212<\/sup> Dimers in Solution: Solvation and Stability Assessed through Molecular Dynamics Simulations"],"prefix":"10.1002","volume":"22","author":[{"given":"Mar\u00e7al","family":"Capdevila\u2010Cortada","sequence":"first","affiliation":[{"name":"Departament de Ci\u00e8ncia de Materials i Qu\u00edmica F\u00edsica and IQTCUB Facultat de Qu\u00edmica Universitat de Barcelona  Av. Diagonal 645 08028 Barcelona Spain"},{"name":"Laboratoire MSM UMR CNRS 7140 Institut de Chimie  4 rue B. Pascal 67000 Strasbourg France"},{"name":"Institute of Chemical Research of Catalonia (ICIQ) The Barcelona Institute of Science and Technology  Av. Pa\u00efsos Catalans 16 43007 Tarragona Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jordi","family":"Ribas\u2010Arino","sequence":"additional","affiliation":[{"name":"Departament de Ci\u00e8ncia de Materials i Qu\u00edmica F\u00edsica and IQTCUB Facultat de Qu\u00edmica Universitat de Barcelona  Av. Diagonal 645 08028 Barcelona Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Alain","family":"Chaumont","sequence":"additional","affiliation":[{"name":"Laboratoire MSM UMR CNRS 7140 Institut de Chimie  4 rue B. Pascal 67000 Strasbourg France"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Georges","family":"Wipff","sequence":"additional","affiliation":[{"name":"Laboratoire MSM UMR CNRS 7140 Institut de Chimie  4 rue B. 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