Presentation + Paper
20 August 2015 Surface-enhanced, multi-dimensional attenuated total reflectance spectroscopy
Jan Philip Kraack, Davide Lotti, Peter Hamm
Author Affiliations +
Abstract
Ultrafast two-dimensional infrared spectroscopy (2D IR) spectroscopy is performed in attenuated total reflectance (ATR) geometry with the Kretschmann configuration in order to measure femtosecond to picosecond dynamics of self-assembled monolayers on gold-coated solid-liquid interfaces. In the monolayers low-absorbing (<200 M-1 cm-1) nitrile functional groups are used as local vibrational probes to monitor vibrational relaxation and spectral diffusion in dependence of different environments of the nitrile group. By comparing spectral diffusion dynamics of the vibrational probe in bulk solution and in the monolayer we find that the dynamics are slowed down by more than a factor of 20 upon immobilization of the sample. Moreover, spectral diffusion dynamics are affected by the local environment within the monolayers as evidenced by 2D ATR IR experiments on mixed monolayers with different aliphatic and aromatic co-adsorbates. The results are interpreted in terms of absent excitation energy-transfer as well as solvation dynamics around the nitrile vibrational probe. Our results demonstrate that 2D ATR IR spectroscopy offers the possibility to obtain ultrafast dynamics from sub-monolayer coverages of even low-absorbing vibrational probes such as nitrile functional groups.
Conference Presentation
© (2015) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only.
Jan Philip Kraack, Davide Lotti, and Peter Hamm "Surface-enhanced, multi-dimensional attenuated total reflectance spectroscopy", Proc. SPIE 9549, Physical Chemistry of Interfaces and Nanomaterials XIV, 95490S (20 August 2015); https://doi.org/10.1117/12.2185533
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CITATIONS
Cited by 10 scholarly publications.
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KEYWORDS
Infrared spectroscopy

Attenuated total reflectance

Diffusion

Spectroscopy

Interfaces

Picosecond phenomena

Ultrafast laser spectroscopy

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