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Correlating the motion of electrons and nuclei with two-dimensional electronic-vibrational spectroscopy

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Correlating the motion of electrons and nuclei with two-dimensional electronic-vibrational spectroscopy. / Oliver, Thomas A A; Lewis, Nicholas H C; Fleming, Graham R.

In: Proceedings of the National Academy of Sciences of the United States of America, Vol. 111, No. 28, 15.07.2014, p. 10061-6.

Research output: Contribution to journalArticle

Harvard

Oliver, TAA, Lewis, NHC & Fleming, GR 2014, 'Correlating the motion of electrons and nuclei with two-dimensional electronic-vibrational spectroscopy', Proceedings of the National Academy of Sciences of the United States of America, vol. 111, no. 28, pp. 10061-6. https://doi.org/10.1073/pnas.1409207111

APA

Oliver, T. A. A., Lewis, N. H. C., & Fleming, G. R. (2014). Correlating the motion of electrons and nuclei with two-dimensional electronic-vibrational spectroscopy. Proceedings of the National Academy of Sciences of the United States of America, 111(28), 10061-6. https://doi.org/10.1073/pnas.1409207111

Vancouver

Oliver TAA, Lewis NHC, Fleming GR. Correlating the motion of electrons and nuclei with two-dimensional electronic-vibrational spectroscopy. Proceedings of the National Academy of Sciences of the United States of America. 2014 Jul 15;111(28):10061-6. https://doi.org/10.1073/pnas.1409207111

Author

Oliver, Thomas A A ; Lewis, Nicholas H C ; Fleming, Graham R. / Correlating the motion of electrons and nuclei with two-dimensional electronic-vibrational spectroscopy. In: Proceedings of the National Academy of Sciences of the United States of America. 2014 ; Vol. 111, No. 28. pp. 10061-6.

Bibtex

@article{94fdcffeea524651b4737ace80e06bbb,
title = "Correlating the motion of electrons and nuclei with two-dimensional electronic-vibrational spectroscopy",
abstract = "Multidimensional nonlinear spectroscopy, in the electronic and vibrational regimes, has reached maturity. To date, no experimental technique has combined the advantages of 2D electronic spectroscopy and 2D infrared spectroscopy, monitoring the evolution of the electronic and nuclear degrees of freedom simultaneously. The interplay and coupling between the electronic state and vibrational manifold is fundamental to understanding ensuing nonradiative pathways, especially those that involve conical intersections. We have developed a new experimental technique that is capable of correlating the electronic and vibrational degrees of freedom: 2D electronic-vibrational spectroscopy (2D-EV). We apply this new technique to the study of the 4-(di-cyanomethylene)-2-methyl-6-p-(dimethylamino)styryl-4H-pyran (DCM) laser dye in deuterated dimethyl sulfoxide and its excited state relaxation pathways. From 2D-EV spectra, we elucidate a ballistic mechanism on the excited state potential energy surface whereby molecules are almost instantaneously projected uphill in energy toward a transition state between locally excited and charge-transfer states, as evidenced by a rapid blue shift on the electronic axis of our 2D-EV spectra. The change in minimum energy structure in this excited state nonradiative crossing is evident as the central frequency of a specific vibrational mode changes on a many-picoseconds timescale. The underlying electronic dynamics, which occur on the hundreds of femtoseconds timescale, drive the far slower ensuing nuclear motions on the excited state potential surface, and serve as a excellent illustration for the unprecedented detail that 2D-EV will afford to photochemical reaction dynamics.",
author = "Oliver, {Thomas A A} and Lewis, {Nicholas H C} and Fleming, {Graham R}",
year = "2014",
month = "7",
day = "15",
doi = "10.1073/pnas.1409207111",
language = "English",
volume = "111",
pages = "10061--6",
journal = "Proceedings of the National Academy of Sciences of the United States of America",
issn = "0027-8424",
publisher = "National Academy of Sciences",
number = "28",

}

RIS - suitable for import to EndNote

TY - JOUR

T1 - Correlating the motion of electrons and nuclei with two-dimensional electronic-vibrational spectroscopy

AU - Oliver, Thomas A A

AU - Lewis, Nicholas H C

AU - Fleming, Graham R

PY - 2014/7/15

Y1 - 2014/7/15

N2 - Multidimensional nonlinear spectroscopy, in the electronic and vibrational regimes, has reached maturity. To date, no experimental technique has combined the advantages of 2D electronic spectroscopy and 2D infrared spectroscopy, monitoring the evolution of the electronic and nuclear degrees of freedom simultaneously. The interplay and coupling between the electronic state and vibrational manifold is fundamental to understanding ensuing nonradiative pathways, especially those that involve conical intersections. We have developed a new experimental technique that is capable of correlating the electronic and vibrational degrees of freedom: 2D electronic-vibrational spectroscopy (2D-EV). We apply this new technique to the study of the 4-(di-cyanomethylene)-2-methyl-6-p-(dimethylamino)styryl-4H-pyran (DCM) laser dye in deuterated dimethyl sulfoxide and its excited state relaxation pathways. From 2D-EV spectra, we elucidate a ballistic mechanism on the excited state potential energy surface whereby molecules are almost instantaneously projected uphill in energy toward a transition state between locally excited and charge-transfer states, as evidenced by a rapid blue shift on the electronic axis of our 2D-EV spectra. The change in minimum energy structure in this excited state nonradiative crossing is evident as the central frequency of a specific vibrational mode changes on a many-picoseconds timescale. The underlying electronic dynamics, which occur on the hundreds of femtoseconds timescale, drive the far slower ensuing nuclear motions on the excited state potential surface, and serve as a excellent illustration for the unprecedented detail that 2D-EV will afford to photochemical reaction dynamics.

AB - Multidimensional nonlinear spectroscopy, in the electronic and vibrational regimes, has reached maturity. To date, no experimental technique has combined the advantages of 2D electronic spectroscopy and 2D infrared spectroscopy, monitoring the evolution of the electronic and nuclear degrees of freedom simultaneously. The interplay and coupling between the electronic state and vibrational manifold is fundamental to understanding ensuing nonradiative pathways, especially those that involve conical intersections. We have developed a new experimental technique that is capable of correlating the electronic and vibrational degrees of freedom: 2D electronic-vibrational spectroscopy (2D-EV). We apply this new technique to the study of the 4-(di-cyanomethylene)-2-methyl-6-p-(dimethylamino)styryl-4H-pyran (DCM) laser dye in deuterated dimethyl sulfoxide and its excited state relaxation pathways. From 2D-EV spectra, we elucidate a ballistic mechanism on the excited state potential energy surface whereby molecules are almost instantaneously projected uphill in energy toward a transition state between locally excited and charge-transfer states, as evidenced by a rapid blue shift on the electronic axis of our 2D-EV spectra. The change in minimum energy structure in this excited state nonradiative crossing is evident as the central frequency of a specific vibrational mode changes on a many-picoseconds timescale. The underlying electronic dynamics, which occur on the hundreds of femtoseconds timescale, drive the far slower ensuing nuclear motions on the excited state potential surface, and serve as a excellent illustration for the unprecedented detail that 2D-EV will afford to photochemical reaction dynamics.

U2 - 10.1073/pnas.1409207111

DO - 10.1073/pnas.1409207111

M3 - Article

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EP - 10066

JO - Proceedings of the National Academy of Sciences of the United States of America

JF - Proceedings of the National Academy of Sciences of the United States of America

SN - 0027-8424

IS - 28

ER -