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タイトル: | Study of Perfluoroalkyl Chain-Specific Band Shift in Infrared Spectra on the Chain Length |
著者: | Shimoaka, Takafumi https://orcid.org/0000-0001-9131-9831 (unconfirmed) Sonoyama, Masashi Amii, Hideki Takagi, Toshiyuki Kanamori, Toshiyuki Hasegawa, Takeshi https://orcid.org/0000-0001-5574-9869 (unconfirmed) |
著者名の別形: | 下赤, 卓史 長谷川, 健 |
キーワード: | Physical and Theoretical Chemistry |
発行日: | 9-Nov-2017 |
出版者: | American Chemical Society (ACS) |
誌名: | The Journal of Physical Chemistry A |
巻: | 121 |
号: | 44 |
開始ページ: | 8425 |
終了ページ: | 8431 |
抄録: | The CF2 symmetric stretching vibration (νs(CF2)) band of a perfluoroalkyl (Rf) group in an infrared (IR) spectrum exhibits a unique character, i.e., an apparent high wavenumber shift with increasing the chain length, which is an opposite character to that of the CH stretching vibration band of a normal alkyl chain. To reveal the mechanism of the unusual IR band shift, two vibrational characters of an Rf chain are focused: (1) a helical conformation of an Rf chain, (2) the carbon (C) atoms having a smaller mass than the fluorine (F) atom dominantly vibrate as a coupled oscillator leaving F atoms stay relatively unmoved. These indicate that a ‘coupled oscillation of the skeletal C atoms’ of an Rf chain should be investigated considering the helical structure. In the present study, therefore, the coupled oscillation of the Rf chain dependent on the chain length is investigated by Raman spectroscopy, which is suitable for investigating a skeletal vibration. The Raman active νs(CF2) band is found to be split into two bands, and the splitting is readily explained by considering the helical structure and length with respect to group theory, and the unusual IR peak shift is concluded to be explained by the helical length. |
著作権等: | This document is the Accepted Manuscript version of a Published Work that appeared in final form in 'The Journal of Physical Chemistry A', copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpca.7b08940 The full-text file will be made open to the public on 5 October 2018 in accordance with publisher's 'Terms and Conditions for Self-Archiving' This is not the published version. Please cite only the published version. この論文は出版社版でありません。引用の際には出版社版をご確認ご利用ください。 |
URI: | http://hdl.handle.net/2433/227882 |
DOI(出版社版): | 10.1021/acs.jpca.7b08940 |
PubMed ID: | 28981281 |
出現コレクション: | 学術雑誌掲載論文等 |
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