Recently, two-dimensional (2D) electronic spectroscopy has become an important tool to unravel the excited state properties of complex molecular assemblies, such as biological light harvesting systems. In this work, we propose a method for simulating 2D electronic spectra based on a surface hopping approach. This approach self-consistently describes the interaction between photoactive chromophores and the environment, which allows us to reproduce a spectrally observable dynamic Stokes shift. Through an application to a dimer, the method is shown to also account for correct thermal equilibration of quantum populations, something that is of great importance for processes in the electronic domain. The resulting 2D spectra are found to nicely agree with hierarchy of equations of motion calculations. Contrary to the latter, our method is unrestricted in describing the interaction between the chromophores and the environment, and we expect it to be applicable to a wide variety of molecular systems.
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28 April 2013
Research Article|
April 23 2013
Surface hopping modeling of two-dimensional spectra Available to Purchase
Roel Tempelaar;
Roel Tempelaar
Zernike Institute for Advanced Materials,
University of Groningen
, Nijenborgh 4, 9747 AG Groningen, The Netherlands
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Cornelis P. van der Vegte;
Cornelis P. van der Vegte
Zernike Institute for Advanced Materials,
University of Groningen
, Nijenborgh 4, 9747 AG Groningen, The Netherlands
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Jasper Knoester;
Jasper Knoester
Zernike Institute for Advanced Materials,
University of Groningen
, Nijenborgh 4, 9747 AG Groningen, The Netherlands
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Thomas L. C. Jansen
Thomas L. C. Jansen
a)
Zernike Institute for Advanced Materials,
University of Groningen
, Nijenborgh 4, 9747 AG Groningen, The Netherlands
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Roel Tempelaar
Cornelis P. van der Vegte
Jasper Knoester
Thomas L. C. Jansen
a)
Zernike Institute for Advanced Materials,
University of Groningen
, Nijenborgh 4, 9747 AG Groningen, The Netherlands
J. Chem. Phys. 138, 164106 (2013)
Article history
Received:
January 30 2013
Accepted:
March 28 2013
Citation
Roel Tempelaar, Cornelis P. van der Vegte, Jasper Knoester, Thomas L. C. Jansen; Surface hopping modeling of two-dimensional spectra. J. Chem. Phys. 28 April 2013; 138 (16): 164106. https://doi.org/10.1063/1.4801519
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