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A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy

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A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy. / Lewis, Nicholas H C; Dong, Hui; Oliver, Thomas A A; Fleming, Graham R.

In: Journal of Chemical Physics, Vol. 143, 28.09.2015, p. 124203-1-124203-13.

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Lewis, Nicholas H C ; Dong, Hui ; Oliver, Thomas A A ; Fleming, Graham R. / A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy. In: Journal of Chemical Physics. 2015 ; Vol. 143. pp. 124203-1-124203-13.

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@article{697ca11df12040c886e86cbb3e1c4646,
title = "A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy",
abstract = "Two dimensional electronic spectroscopy has proved to be a valuable experimental technique to reveal electronic excitation dynamics in photosynthetic pigment-protein complexes, nanoscale semiconductors, organic photovoltaic materials, and many other types of systems. It does not, however, provide direct information concerning the spatial structure and dynamics of excitons. 2D infrared spectroscopy has become a widely used tool for studying structural dynamics but is incapable of directly providing information concerning electronic excited states. 2D electronic-vibrational (2DEV) spectroscopy provides a link between these domains, directly connecting the electronic excitation with the vibrational structure of the system under study. In this work, we derive response functions for the 2DEV spectrum of a molecular dimer and propose a method by which 2DEV spectra could be used to directly measure the electronic site populations as a function of time following the initial electronic excitation. We present results from the response function simulations which show that our proposed approach is substantially valid. This method provides, to our knowledge, the first direct experimental method for measuring the electronic excited state dynamics in the spatial domain, on the molecular scale.",
author = "Lewis, {Nicholas H C} and Hui Dong and Oliver, {Thomas A A} and Fleming, {Graham R}",
year = "2015",
month = "9",
day = "28",
doi = "10.1063/1.4931634",
language = "English",
volume = "143",
pages = "124203--1--124203--13",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics (AIP)",

}

RIS - suitable for import to EndNote

TY - JOUR

T1 - A method for the direct measurement of electronic site populations in a molecular aggregate using two-dimensional electronic-vibrational spectroscopy

AU - Lewis, Nicholas H C

AU - Dong, Hui

AU - Oliver, Thomas A A

AU - Fleming, Graham R

PY - 2015/9/28

Y1 - 2015/9/28

N2 - Two dimensional electronic spectroscopy has proved to be a valuable experimental technique to reveal electronic excitation dynamics in photosynthetic pigment-protein complexes, nanoscale semiconductors, organic photovoltaic materials, and many other types of systems. It does not, however, provide direct information concerning the spatial structure and dynamics of excitons. 2D infrared spectroscopy has become a widely used tool for studying structural dynamics but is incapable of directly providing information concerning electronic excited states. 2D electronic-vibrational (2DEV) spectroscopy provides a link between these domains, directly connecting the electronic excitation with the vibrational structure of the system under study. In this work, we derive response functions for the 2DEV spectrum of a molecular dimer and propose a method by which 2DEV spectra could be used to directly measure the electronic site populations as a function of time following the initial electronic excitation. We present results from the response function simulations which show that our proposed approach is substantially valid. This method provides, to our knowledge, the first direct experimental method for measuring the electronic excited state dynamics in the spatial domain, on the molecular scale.

AB - Two dimensional electronic spectroscopy has proved to be a valuable experimental technique to reveal electronic excitation dynamics in photosynthetic pigment-protein complexes, nanoscale semiconductors, organic photovoltaic materials, and many other types of systems. It does not, however, provide direct information concerning the spatial structure and dynamics of excitons. 2D infrared spectroscopy has become a widely used tool for studying structural dynamics but is incapable of directly providing information concerning electronic excited states. 2D electronic-vibrational (2DEV) spectroscopy provides a link between these domains, directly connecting the electronic excitation with the vibrational structure of the system under study. In this work, we derive response functions for the 2DEV spectrum of a molecular dimer and propose a method by which 2DEV spectra could be used to directly measure the electronic site populations as a function of time following the initial electronic excitation. We present results from the response function simulations which show that our proposed approach is substantially valid. This method provides, to our knowledge, the first direct experimental method for measuring the electronic excited state dynamics in the spatial domain, on the molecular scale.

U2 - 10.1063/1.4931634

DO - 10.1063/1.4931634

M3 - Article

VL - 143

SP - 124203-1-124203-13

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

ER -