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8 - Dynamic cross-peaks

Published online by Cambridge University Press:  05 August 2012

Peter Hamm
Affiliation:
Universität Zürich
Martin Zanni
Affiliation:
University of Wisconsin, Madison
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Summary

In Chapter 7 we found that a time dependent Hamiltonian (Eq. 7.2) is the source of infrared lineshapes. It also causes energy transfer between eigenstates that will alter the intensity of cross- and diagonal peaks or create completely new peaks. As for lineshapes, the time dependence of the Hamiltonian results from the fluctuations of the solvent and molecular structure. Three types of relaxation occur, all of which have been observed experimentally: population relaxation, population transfer, and coherence transfer. Figure 8.1 shows an example of a Feynman diagram for each of these cases. In contrast to the Feynman diagrams that we have seen so far, these diagrams time-propagate with more than just the usual oscillatory terms. They flip quantum states (indicated by the dotted lines and the arrows in Fig. 8.1). Population relaxation, population transfer, and coherence transfer correspond to flipping an excited population state |1〈〉1| back into the ground state |0〈〉0| (Fig. 8.1a), flipping an excited population state |1〈〉1| into another excited state |1'〈〉1'| (Fig. 8.1b), and flipping a coherence state |0〈〉1| into another coherence state |0〈〉1'| (Fig. 8.1c), respectively. A rigorous treatment of relaxation processes has become quite demanding, and we outline here only the simplest cases. For a more comprehensive discussion, we refer readers to Ref. [106].

Population transfer

As the simplest case, consider a dimer of coupled oscillators that is sitting in a fluctuating bath.

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Publisher: Cambridge University Press
Print publication year: 2011

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  • Dynamic cross-peaks
  • Peter Hamm, Universität Zürich, Martin Zanni, University of Wisconsin, Madison
  • Book: Concepts and Methods of 2D Infrared Spectroscopy
  • Online publication: 05 August 2012
  • Chapter DOI: https://doi.org/10.1017/CBO9780511675935.008
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  • Dynamic cross-peaks
  • Peter Hamm, Universität Zürich, Martin Zanni, University of Wisconsin, Madison
  • Book: Concepts and Methods of 2D Infrared Spectroscopy
  • Online publication: 05 August 2012
  • Chapter DOI: https://doi.org/10.1017/CBO9780511675935.008
Available formats
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Save book to Google Drive

To save content items to your account, please confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your account. Find out more about saving content to Google Drive.

  • Dynamic cross-peaks
  • Peter Hamm, Universität Zürich, Martin Zanni, University of Wisconsin, Madison
  • Book: Concepts and Methods of 2D Infrared Spectroscopy
  • Online publication: 05 August 2012
  • Chapter DOI: https://doi.org/10.1017/CBO9780511675935.008
Available formats
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