High Frequency Vibrational Modulations in Two-Dimensional Electronic Spectra and Their Resemblance to Electronic Coherence Signatures

Autor(en)

Niklas Christensson, Franz Milota, Jürgen Hauer, Jaroslaw Sperling, Oliver Bixner, Alexandra Nemeth, Harald F Kauffmann

Abstrakt

In this work we analyze how nuclear coherences modulate diagonal and off-diagonal peaks in two-dimensional electronic spectroscopy. 2D electronic spectra of pinacyanol chloride are measured with 8 fs pulses, which allows coherent excitation of the 1300 cm(-1) vibrational mode. The 2D spectrum reveals both diagonal and off-diagonal peaks related to the vibrational mode. On early time scales, up to 30 fs, coherent dynamics give rise to oscillations in the amplitudes, positions, and shapes of the peaks in the 2D spectrum. We find an anticorrelation between the amplitude and the diagonal width of the two diagonal peaks. The measured data are reproduced with a model incorporating a high frequency mode coupled to an electronic two-level-system. Our results show that these anti-correlated oscillations occur for vibrational wavepackets and not exclusively for electronic coherences as has been assumed previously.

Organisation(en)

Elektronische Materialeigenschaften

Externe Organisation(en)

Ludwig-Maximilians-Universität München, Technische Universität Wien

Journal

The Journal of Physical Chemistry Part B: Condensed Matter, Materials, Surfaces, Interfaces & Biophysical

Band

115

Seiten

5383-5391

Anzahl der Seiten

9

ISSN

1520-6106

DOI

https://doi.org/10.1021/jp109442b

Publikationsdatum

2011

Peer-reviewed

Ja

ÖFOS 2012

104017 Physikalische Chemie, 103018 Materialphysik

Link zum Portal

https://ucrisportal.univie.ac.at/de/publications/cfeecf5b-e7f9-42b6-8c6d-3f88a5dc7f00