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.
Structure and chain polarization of long polyynes investigated with infrared and Raman spectroscopy†
Version of Record online: 27 MAY 2013
Copyright © 2013 John Wiley & Sons, Ltd.
Journal of Raman Spectroscopy
Special Issue: Joint special issue on the European Conference on Nonlinear Optical Spectroscopy (ECONOS 2012) and the II Italian Conference of the National Group of Raman Spectroscopy and Non-Linear Effects (GISR 2012)
Volume 44, Issue 10, pages 1398–1410, October 2013
How to Cite
Agarwal, N. R., Lucotti, A., Fazzi, D., Tommasini, M., Castiglioni, C., Chalifoux, W.A. and Tykwinski, R. R. (2013), Structure and chain polarization of long polyynes investigated with infrared and Raman spectroscopy. J. Raman Spectrosc., 44: 1398–1410. doi: 10.1002/jrs.4300
- Issue online: 22 OCT 2013
- Version of Record online: 27 MAY 2013
- Manuscript Accepted: 14 MAR 2013
- Manuscript Revised: 14 FEB 2013
- Manuscript Received: 30 OCT 2012
- Ministero dell'Istruzione, dell'Università e della Ricerca
- PRIN Project 2008
- Deutsche Forschungsgemeinschaft
- sp-carbon chains;
- Raman and IR spectroscopy;
- density functional theory calculations
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 CC 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.