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Issue 26, 2019
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Two-dimensional electronic-vibrational spectroscopic study of conical intersection dynamics: an experimental and electronic structure study

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Abstract

The relaxation from the lowest singlet excited state of the triphenylmethane dyes, crystal violet and malachite green, is studied via two-dimensional electronic-vibrational (2DEV) spectroscopy. After excitation of the dyes at their respective absorption maxima, the ensuing excited state dynamics are tracked by monitoring the C[double bond, length as m-dash]C aromatic stretch. With the aid of electronic structure calculations, the observed transitions in the 2DEV spectra are assigned to specific geometries and a detailed story of the evolution of the nuclear wavepacket as it diffuses on the excited state potential energy surface (PES) and ultimately passes through the conical intersection is developed. Notably, it is revealed that the relaxation of the lowest singlet excited state involves intramolecular charge transfer while the nuclear wavepacket is on the excited state PES. Finally, through analyzing the center line slopes of the measured peaks, we show how both solvent motions and changes in the molecular dipole moment affect the correlation between electronic and vibrational degrees of freedom. This work clearly demonstrates the usefulness of 2DEV spectroscopy in following the motion of nuclear wavepackets after photoexcitation and in studying the interactions between the molecular dipole moment and surrounding solvent environment.

Graphical abstract: Two-dimensional electronic-vibrational spectroscopic study of conical intersection dynamics: an experimental and electronic structure study

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Supplementary files

Article information


Submitted
17 Aug 2018
Accepted
04 Oct 2018
First published
04 Oct 2018

Phys. Chem. Chem. Phys., 2019,21, 14153-14163
Article type
Paper
Author version available

Two-dimensional electronic-vibrational spectroscopic study of conical intersection dynamics: an experimental and electronic structure study

E. C. Wu, Q. Ge, E. A. Arsenault, N. H. C. Lewis, N. L. Gruenke, M. J. Head-Gordon and G. R. Fleming, Phys. Chem. Chem. Phys., 2019, 21, 14153
DOI: 10.1039/C8CP05264F

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