論文

査読有り
2015年4月

Photodetachment Spectroscopy of Fluorenone Radical Anions Microsolvated with Methanol: Rationalizing the Anomalous Solvatochromic Behavior Due to Hydrogen Bonding

JOURNAL OF PHYSICAL CHEMISTRY A
  • Toshihiko Maeyama
  • ,
  • Izumi Yagi
  • ,
  • Keiji Yoshida
  • ,
  • Asuka Fujii
  • ,
  • Naohiko Mikami

119
16
開始ページ
3721
終了ページ
3730
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1021/acs.jpca.5b01147
出版者・発行元
AMER CHEMICAL SOC

The attribution of the extraordinary blue shift for the intramolecular charge-transfer absorption band of fluorenone radical anion solvated in profit media was investigated by meats of photodetachment spectroscopy of the gas-phase anions microsolvated with methanol in conjunction with quantum chemical calculations based on density functional theory. Sequential shifts of the vertical detachment energy as a function of the cluster size are consistent with theoretical predictions, where up to two methanol molecules can directly attach to the carbonyl group. In the photodetachment excitation spectra as alternatives to the photoabsorption spectra, with increasing duster size, a new absorption band grows in the higher-energy region, which coincides with the blue-shifted band in protic media. Spectral simulations using time-dependent density functional theory with the CAM-B3LYP functional reproduced the feature of the phenomenon. Analyses on the electronic configuration elucidated that the extraordinarily blue shifts originate from energy-level repulsion due to solvation-induced resonant coupling with another electronic state. The orbital transition for the counterpart state corresponds to the first absorption band of the neutral fluorenone molecule, which has small oscillator strength from the ground state. It was found that correction of long-range electron exchange correlation is important for the spectral simulation involving the electronic-state coupling.

リンク情報
DOI
https://doi.org/10.1021/acs.jpca.5b01147
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000353604300004&DestApp=WOS_CPL
ID情報
  • DOI : 10.1021/acs.jpca.5b01147
  • ISSN : 1089-5639
  • Web of Science ID : WOS:000353604300004

エクスポート
BibTeX RIS