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Electronic Structure and Redox Properties of Metal Nitride Endohedral Fullerenes M3N@C2n (M=Sc,Y, La,and Gd; 2n=80, 84, 88, 92, 96)
Authors:Ramón Valencia  Antonio Rodríguez‐Fortea Dr.  Anna Clotet Dr.  Coen de Graaf Dr.  Manuel N. Chaur  Luis Echegoyen Prof. Dr.  Josep M. Poblet Prof. Dr.
Affiliation:1. Departament de Química Física i Inorgànica, Universitat Rovira i Virgili c/Marcel?lí Domingo s/n, Campus Sescelades, 43007 Tarragona (Spain), Fax: (+34)?977‐559‐563;2. Institució Catalana de Recerca i Estudis Avan?ats (ICREA), Passeig Lluís Companys 23, 08010 Barcelona (Spain);3. Department of Chemistry, Clemson University, 219 Hunter Laboratories, Clemson, SC 29634 (USA)
Abstract:An extensive study of the redox properties of metal nitride endohedral fullerenes (MNEFs) based on DFT computational calculations has been performed. The electronic structure of the singly oxidized and reduced MNEFs has been thoroughly analyzed and the first anodic and cathodic potentials, as well as the electrochemical gaps, have been predicted for a large number of M3N@C2n systems (M=Sc, Y, La, and Gd; 2n=80, 84, 88, 92, and 96). In particular, calculations that include thermal and entropic effects correctly predict the different anodic behavior of the two isomers (Ih and D5h) of Sc3N@C80, which is the basis for their electrochemical separation. Important differences were found in the electronic structure of reduced M3N@C80 when M=Sc or when M is a more electropositive metal, such as Y or Gd. Moreover, the changes in the electrochemical gaps within the Gd3N@C2n series (2n=80, 84, and 88) have been rationalized and the use of Y‐based computational models to study the Gd‐based systems has been justified. The redox properties of the largest MNEFs characterized so far, La3N@C2n (2n=92 and 96), were also correctly predicted. Finally, the quality of these predictions and their usefulness in distinguishing the carbon cages for MNEFs with unknown structures is discussed.
Keywords:density functional calculations  electrochemistry  fullerenes  HOMO–  LUMO gap  metal nitride clusters
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