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Origin of reactivity trends of noble gas endohedral fullerenes Ng2atC60(Ng = He to Xe)

We have computationally studied the factors governing the enhanced Diels-Alder reactivity of noble gas endohedral fullerenes Ng2@C60when Ng = Ar, Kr, and Xe as compared to Ng = none, He, and Ne. To this end, we have employed the activation strain model of reactivity in combination with the energy decomposition analysis (EDA) method in DFT calculations on the Diels-Alder cycloaddition reaction between Ng2@C60and 1,3-butadiene. Our results indicate that when heavier noble gas dimers are introduced inside the C60cage, dramatic effects on both the geometrical and electronic structure of the fullerenic cage occur leading to a remarkable enhanced interaction between the deformed reactants along the entire reaction coordinate

We are grateful for financial support from the Spanish MINECO (Grants CTQ2010-20714-C02-01, Consolider-Ingenio 2010, and CSD2007-00006 to I.F. and CTQ2011-23156/BQU to M.S.), CAM (S2009/PPQ-1634 to I.F.), Catalan DIUE (projects 2009SGR637 and XRQTC to M.S.), the FEDER fund for the grant UNGI08-4 X 10-003 to M.S., the National Research School Combination - Catalysis (NRSC-C), and The Netherlands Organization for Scientific Research (NVVO/CW and NVVO/EW)

© Journal of Chemical Theory and Computation, 2014, vol. 10, núm. 9, p. 3863-3870

American Chemical Society (ACS)

Author: Fernández, Israel
Solà i Puig, Miquel
Bickelhaupt, Friedrich Matthias
Date: 2014
Abstract: We have computationally studied the factors governing the enhanced Diels-Alder reactivity of noble gas endohedral fullerenes Ng2@C60when Ng = Ar, Kr, and Xe as compared to Ng = none, He, and Ne. To this end, we have employed the activation strain model of reactivity in combination with the energy decomposition analysis (EDA) method in DFT calculations on the Diels-Alder cycloaddition reaction between Ng2@C60and 1,3-butadiene. Our results indicate that when heavier noble gas dimers are introduced inside the C60cage, dramatic effects on both the geometrical and electronic structure of the fullerenic cage occur leading to a remarkable enhanced interaction between the deformed reactants along the entire reaction coordinate
We are grateful for financial support from the Spanish MINECO (Grants CTQ2010-20714-C02-01, Consolider-Ingenio 2010, and CSD2007-00006 to I.F. and CTQ2011-23156/BQU to M.S.), CAM (S2009/PPQ-1634 to I.F.), Catalan DIUE (projects 2009SGR637 and XRQTC to M.S.), the FEDER fund for the grant UNGI08-4 X 10-003 to M.S., the National Research School Combination - Catalysis (NRSC-C), and The Netherlands Organization for Scientific Research (NVVO/CW and NVVO/EW)
Format: application/pdf
ISSN: 1549-9618 (versió paper)
1549-9626 (versió electrònica)
Document access: http://hdl.handle.net/10256/11423
Language: eng
Publisher: American Chemical Society (ACS)
Collection: MICINN/PN 2012-2014/CTQ2011-23156
AGAUR/2009-2014/2009 SGR-637
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/ct500444z
Articles publicats (D-Q)
Is part of: © Journal of Chemical Theory and Computation, 2014, vol. 10, núm. 9, p. 3863-3870
Rights: Tots els drets reservats
Subject: Ful·lerens -- Reactivitat
Fullerenes -- Reactivity
Reaccions químiques
Chemical reactions
Diels-Alder, Reacció de
Title: Origin of reactivity trends of noble gas endohedral fullerenes Ng2atC60(Ng = He to Xe)
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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