2000年4月
Cage dynamics in the third-order off-resonant response of liquid molecules: A theoretical realization
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
- ,
- ,
- 巻
- 73
- 号
- 4
- 開始ページ
- 873
- 終了ページ
- 884
- 記述言語
- 英語
- 掲載種別
- 研究論文(学術雑誌)
- DOI
- 10.1246/bcsj.73.873
- 出版者・発行元
- CHEMICAL SOC JAPAN
It is generally believed that the ultrafast initial spectroscopic response from the molecules in the condensed phase originates from small amplitude inertial motions within the cage formed by the nearest-neighbor solvent molecules surrounding the probe, or the cage effect. However, no quantitative estimate of this dynamics has been available for the currently popular experiments which measure the third-order off-resonant response. In this work, we fill this gap by a microscopic approach and demonstrate that the cage dynamics alone can produce the initial rise in the subpicosecond (ca. 200 fs) range in the third-order response. A simple analytical expression for the initial Gaussian time constant relevant to various kinds of the third-order off-resonant experiments is presented, which is found to be rather strongly dependent on the temperature. Connection with the non-polar solvation dynamics is also discussed.
- リンク情報
- ID情報
-
- DOI : 10.1246/bcsj.73.873
- ISSN : 0009-2673
- eISSN : 1348-0634
- CiNii Articles ID : 10009146464
- Web of Science ID : WOS:000086860900013