Volume 122, 2003

Femtosecond mid-infrared spectroscopy of condensed phase hydrogen-bonded systems as a probe of structural dynamics

Abstract

We report the first time-resolved site-specific mid-infrared study of the photo-induced excited state hydrogen transfer reaction in 2-(2′-hydroxyphenyl)benzothiazole (HBT) with 130 fs time resolution. The transient absorption of the C[double bond, length half m-dash]O stretching band marking the keto*-S1-state appears delayed on a time scale of 30–50 fs after electronic excitation to the enol*-S1-state. Its line center subsequently shifts up by about 3–5 cm−1 after excitation, depending on the excitation wavelength tuned between 315 and 349 nm. This effect is attributed to intramolecular vibrational energy redistribution (IVR) and vibrational energy relaxation (VER) processes. We observe for the first time the coherent effects of anharmonic coupling of low frequency modes (≈60 cm−1, ≈120 cm−1), on the C[double bond, length half m-dash]O mode marking the product state. We ascribe the 120 cm−1 mode to a Raman-active in-plane deformation mode that is coherently excited by the UV-pump pulse. We tentatively explain the coherent excitation of the infrared active 60 cm−1 out-of-plane deformation mode by nonradiative processes within the excited enol state after electronic excitation.

Article information

Article type
Paper
Submitted
29 Jan 2002
Accepted
12 Apr 2002
First published
18 Jul 2002

Faraday Discuss., 2003,122, 27-40

Femtosecond mid-infrared spectroscopy of condensed phase hydrogen-bonded systems as a probe of structural dynamics

M. Rini, A. Kummrow, J. Dreyer, E. T. J. Nibbering and T. Elsaesser, Faraday Discuss., 2003, 122, 27 DOI: 10.1039/B201056A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements