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Determining the static electronic and vibrational energy correlations via two-dimensional electronic-vibrational spectroscopy

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Determining the static electronic and vibrational energy correlations via two-dimensional electronic-vibrational spectroscopy. / Dong, Hui; Lewis, Nicholas H C; Oliver, Thomas A A; Fleming, Graham R.

In: Journal of Chemical Physics, Vol. 142, No. 17, 07.05.2015, p. 174201.

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Dong, Hui ; Lewis, Nicholas H C ; Oliver, Thomas A A ; Fleming, Graham R. / Determining the static electronic and vibrational energy correlations via two-dimensional electronic-vibrational spectroscopy. In: Journal of Chemical Physics. 2015 ; Vol. 142, No. 17. pp. 174201.

Bibtex

@article{52d030cd76d84af0949f037b92de7b3d,
title = "Determining the static electronic and vibrational energy correlations via two-dimensional electronic-vibrational spectroscopy",
abstract = "Changes in the electronic structure of pigments in protein environments and of polar molecules in solution inevitably induce a re-adaption of molecular nuclear structure. Both changes of electronic and vibrational energies can be probed with visible or infrared lasers, such as two-dimensional electronic spectroscopy or vibrational spectroscopy. The extent to which the two changes are correlated remains elusive. The recent demonstration of two-dimensional electronic-vibrational (2DEV) spectroscopy potentially enables a direct measurement of this correlation experimentally. However, it has hitherto been unclear how to characterize the correlation from the spectra. In this paper, we present a theoretical formalism to demonstrate the slope of the nodal line between the excited state absorption and ground state bleach peaks in the spectra as a characterization of the correlation between electronic and vibrational transition energies. We also show the dynamics of the nodal line slope is correlated to the vibrational spectral dynamics. Additionally, we demonstrate the fundamental 2DEV spectral line-shape of a monomer with newly developed response functions.",
author = "Hui Dong and Lewis, {Nicholas H C} and Oliver, {Thomas A A} and Fleming, {Graham R}",
year = "2015",
month = "5",
day = "7",
doi = "10.1063/1.4919684",
language = "English",
volume = "142",
pages = "174201",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "17",

}

RIS - suitable for import to EndNote

TY - JOUR

T1 - Determining the static electronic and vibrational energy correlations via two-dimensional electronic-vibrational spectroscopy

AU - Dong, Hui

AU - Lewis, Nicholas H C

AU - Oliver, Thomas A A

AU - Fleming, Graham R

PY - 2015/5/7

Y1 - 2015/5/7

N2 - Changes in the electronic structure of pigments in protein environments and of polar molecules in solution inevitably induce a re-adaption of molecular nuclear structure. Both changes of electronic and vibrational energies can be probed with visible or infrared lasers, such as two-dimensional electronic spectroscopy or vibrational spectroscopy. The extent to which the two changes are correlated remains elusive. The recent demonstration of two-dimensional electronic-vibrational (2DEV) spectroscopy potentially enables a direct measurement of this correlation experimentally. However, it has hitherto been unclear how to characterize the correlation from the spectra. In this paper, we present a theoretical formalism to demonstrate the slope of the nodal line between the excited state absorption and ground state bleach peaks in the spectra as a characterization of the correlation between electronic and vibrational transition energies. We also show the dynamics of the nodal line slope is correlated to the vibrational spectral dynamics. Additionally, we demonstrate the fundamental 2DEV spectral line-shape of a monomer with newly developed response functions.

AB - Changes in the electronic structure of pigments in protein environments and of polar molecules in solution inevitably induce a re-adaption of molecular nuclear structure. Both changes of electronic and vibrational energies can be probed with visible or infrared lasers, such as two-dimensional electronic spectroscopy or vibrational spectroscopy. The extent to which the two changes are correlated remains elusive. The recent demonstration of two-dimensional electronic-vibrational (2DEV) spectroscopy potentially enables a direct measurement of this correlation experimentally. However, it has hitherto been unclear how to characterize the correlation from the spectra. In this paper, we present a theoretical formalism to demonstrate the slope of the nodal line between the excited state absorption and ground state bleach peaks in the spectra as a characterization of the correlation between electronic and vibrational transition energies. We also show the dynamics of the nodal line slope is correlated to the vibrational spectral dynamics. Additionally, we demonstrate the fundamental 2DEV spectral line-shape of a monomer with newly developed response functions.

U2 - 10.1063/1.4919684

DO - 10.1063/1.4919684

M3 - Article

VL - 142

SP - 174201

JO - Journal of Chemical Physics

T2 - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 17

ER -