Measurement of electron-electron interactions and correlations using two-dimensional electronic double-quantum coherence spectroscopy

Jeongho Kim, Vanessa Margaret Huxter, Carles Curutchet, Gregory D. Scholes

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

A two-dimensional (2D) optical coherent spectroscopy that correlates the double excited electronic states to constituent single excited states is described. The technique, termed two-dimensional double-quantum coherence spectroscopy (2D-DQCS), makes use of multiple, time-ordered ultrashort coherent optical pulses to create double and single quantum coherences over the time intervals between the pulses. The resulting 2D electronic spectra map out the energy correlation between the first excited state and two-photon-allowed double-quantum states. Measurements of organic dye molecules show that the near-resonant energy offset for adding a second electronic excitation to the system relative to the first excitation is on the order of tens of millielectronvolts. Simulations of DQC spectra show that vibronic transitions add rich features to the 2D spectra. The results of quantum chemical calculations on model systems provide insight into the many-body origin of the energy shift measured in the experiment. These results demonstrate the potential of 2D-DQCS for elucidating quantitative information about electron-electron interactions, many-electron wave functions, and electron correlation in electronic excited states and excitons.

Original languageEnglish (US)
Pages (from-to)12122-12133
Number of pages12
JournalJournal of Physical Chemistry A
Volume113
Issue number44
DOIs
StatePublished - Nov 5 2009
Externally publishedYes

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Electron-electron interactions
Excited states
electron scattering
Spectroscopy
Laser pulses
electronics
spectroscopy
excitation
Electron correlations
electrons
Electronic states
Wave functions
Coloring Agents
Photons
pulses
Molecules
Electrons
electronic spectra
energy
dyes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Measurement of electron-electron interactions and correlations using two-dimensional electronic double-quantum coherence spectroscopy. / Kim, Jeongho; Huxter, Vanessa Margaret; Curutchet, Carles; Scholes, Gregory D.

In: Journal of Physical Chemistry A, Vol. 113, No. 44, 05.11.2009, p. 12122-12133.

Research output: Contribution to journalArticle

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N2 - A two-dimensional (2D) optical coherent spectroscopy that correlates the double excited electronic states to constituent single excited states is described. The technique, termed two-dimensional double-quantum coherence spectroscopy (2D-DQCS), makes use of multiple, time-ordered ultrashort coherent optical pulses to create double and single quantum coherences over the time intervals between the pulses. The resulting 2D electronic spectra map out the energy correlation between the first excited state and two-photon-allowed double-quantum states. Measurements of organic dye molecules show that the near-resonant energy offset for adding a second electronic excitation to the system relative to the first excitation is on the order of tens of millielectronvolts. Simulations of DQC spectra show that vibronic transitions add rich features to the 2D spectra. The results of quantum chemical calculations on model systems provide insight into the many-body origin of the energy shift measured in the experiment. These results demonstrate the potential of 2D-DQCS for elucidating quantitative information about electron-electron interactions, many-electron wave functions, and electron correlation in electronic excited states and excitons.

AB - A two-dimensional (2D) optical coherent spectroscopy that correlates the double excited electronic states to constituent single excited states is described. The technique, termed two-dimensional double-quantum coherence spectroscopy (2D-DQCS), makes use of multiple, time-ordered ultrashort coherent optical pulses to create double and single quantum coherences over the time intervals between the pulses. The resulting 2D electronic spectra map out the energy correlation between the first excited state and two-photon-allowed double-quantum states. Measurements of organic dye molecules show that the near-resonant energy offset for adding a second electronic excitation to the system relative to the first excitation is on the order of tens of millielectronvolts. Simulations of DQC spectra show that vibronic transitions add rich features to the 2D spectra. The results of quantum chemical calculations on model systems provide insight into the many-body origin of the energy shift measured in the experiment. These results demonstrate the potential of 2D-DQCS for elucidating quantitative information about electron-electron interactions, many-electron wave functions, and electron correlation in electronic excited states and excitons.

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