Structure and chain polarization of long polyynes investigated with infrared and Raman spectroscopy

Authors

  • N. R. Agarwal,

    1. Dipartimento di Chimica, Materiali e Ingegneria Chimica ‘G. Natta’, Politecnico di Milano, Milano, Italy
    2. Consorzio Interuniversitario per la Scienza e Tecnologia dei Materiali (INSTM), Unità di Ricerca del Politecnico di Milano (Dip. CMIC), Milano, Italy
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  • A. Lucotti,

    1. Dipartimento di Chimica, Materiali e Ingegneria Chimica ‘G. Natta’, Politecnico di Milano, Milano, Italy
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  • D. Fazzi,

    1. Centre for Nanoscience and Technology – CNST@PoliMi, Italian Institute of Technology, Milano, Italy
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  • M. Tommasini,

    Corresponding author
    1. Dipartimento di Chimica, Materiali e Ingegneria Chimica ‘G. Natta’, Politecnico di Milano, Milano, Italy
    2. Consorzio Interuniversitario per la Scienza e Tecnologia dei Materiali (INSTM), Unità di Ricerca del Politecnico di Milano (Dip. CMIC), Milano, Italy
    • Correspondence to: C. Castiglioni, Dipartimento di Chimica, Materiali e Ingegneria Chimica ‘G. Natta’, Politecnico di Milano, Piazza Leonardo da Vinci 32 – 20133 Milano, Italy. E-mail: chiara.castiglioni@polimi.it

      M. Tommasini, Dipartimento di Chimica, Materiali e Ingegneria Chimica ‘G. Natta’, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy. E-mail: matteo.tommasini@polimi.it

      R. R. Tykwinski, Department of Chemistry and Pharmacy & Interdisciplinary Center of Molecular Materials (ICMM), University of Erlangen-Nuremberg, 91054 Erlangen, Germany. E-mail: rik.tykwinski@chemie.uni-erlangen.de

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  • C. Castiglioni,

    Corresponding author
    1. Dipartimento di Chimica, Materiali e Ingegneria Chimica ‘G. Natta’, Politecnico di Milano, Milano, Italy
    • Correspondence to: C. Castiglioni, Dipartimento di Chimica, Materiali e Ingegneria Chimica ‘G. Natta’, Politecnico di Milano, Piazza Leonardo da Vinci 32 – 20133 Milano, Italy. E-mail: chiara.castiglioni@polimi.it

      M. Tommasini, Dipartimento di Chimica, Materiali e Ingegneria Chimica ‘G. Natta’, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy. E-mail: matteo.tommasini@polimi.it

      R. R. Tykwinski, Department of Chemistry and Pharmacy & Interdisciplinary Center of Molecular Materials (ICMM), University of Erlangen-Nuremberg, 91054 Erlangen, Germany. E-mail: rik.tykwinski@chemie.uni-erlangen.de

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  • W.A. Chalifoux,

    1. Department of Chemistry, University of Nevada, Reno, USA
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  • R. R. Tykwinski

    Corresponding author
    1. Department of Chemistry and Pharmacy & Interdisciplinary Center of Molecular Materials (ICMM), University of Erlangen-Nuremberg, Erlangen, Germany
    • Correspondence to: C. Castiglioni, Dipartimento di Chimica, Materiali e Ingegneria Chimica ‘G. Natta’, Politecnico di Milano, Piazza Leonardo da Vinci 32 – 20133 Milano, Italy. E-mail: chiara.castiglioni@polimi.it

      M. Tommasini, Dipartimento di Chimica, Materiali e Ingegneria Chimica ‘G. Natta’, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy. E-mail: matteo.tommasini@polimi.it

      R. R. Tykwinski, Department of Chemistry and Pharmacy & Interdisciplinary Center of Molecular Materials (ICMM), University of Erlangen-Nuremberg, 91054 Erlangen, Germany. E-mail: rik.tykwinski@chemie.uni-erlangen.de

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  • This article is from the GISR part of the joint special issue on the European Conference on Nonlinear Optical Spectroscopy (ECONOS 2012) with Guest Editors Johannes Kiefer and Peter Radi and the II Italian Conference of the National Group of Raman Spectroscopy and Non-Linear Effects (GISR 2012) with Guest Editor Maria Grazia Giorgini.

Abstract

Symmetrically and unsymmetrically endcapped polyynes (triisopropylsilyl – TIPS – and super trityl endcapping groups) have been studied with density functional theory calculations and Raman and infrared spectroscopy. This spectroscopic investigation provides general guidelines for studying the vibrational and structural features of sp-carbon-based materials, which nowadays are at the center of growing interest for the potential applications of nanostructured carbon materials in molecular electronics. On the basis of the description of C[BOND]C stretching modes of polyynes in terms of longitudinal optical phonons of the parent infinite sp-carbon chain, we have carried out the complete assignment of the observed infrared and Raman features in the 2300–1900 cm−1 range, for chain lengths in the range 4–20 triple bonds. This allows demonstration of polarization effects induced by an unsymmetric structure and deviations from chain linearity in long polyynes. Copyright © 2013 John Wiley & Sons, Ltd.

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