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Title: Two-dimensional vibrational-electronic spectroscopy

Two-dimensional vibrational-electronic (2D VE) spectroscopy is a femtosecond Fourier transform (FT) third-order nonlinear technique that creates a link between existing 2D FT spectroscopies in the vibrational and electronic regions of the spectrum. 2D VE spectroscopy enables a direct measurement of infrared (IR) and electronic dipole moment cross terms by utilizing mid-IR pump and optical probe fields that are resonant with vibrational and electronic transitions, respectively, in a sample of interest. We detail this newly developed 2D VE spectroscopy experiment and outline the information contained in a 2D VE spectrum. We then use this technique and its single-pump counterpart (1D VE) to probe the vibrational-electronic couplings between high frequency cyanide stretching vibrations (ν CN) and either a ligand-to-metal charge transfer transition ([Fe III(CN) 6] 3- dissolved in formamide) or a metal-to-metal charge transfer (MMCT) transition ([(CN) 5Fe IICNRu III(NH 3) 5]- dissolved in formamide). The 2D VE spectra of both molecules reveal peaks resulting from coupled high- and low-frequency vibrational modes to the charge transfer transition. The time-evolving amplitudes and positions of the peaks in the 2D VE spectra report on coherent and incoherent vibrational energy transfer dynamics among the coupled vibrational modes and the charge transfer transition. The selectivity ofmore » 2D VE spectroscopy to vibronic processes is evidenced from the selective coupling of specific ν CN modes to the MMCT transition in the mixed valence complex. The lineshapes in 2D VE spectra report on the correlation of the frequency fluctuations between the coupled vibrational and electronic frequencies in the mixed valence complex which has a time scale of 1 ps. Lastly, the details and results of this study confirm the versatility of 2D VE spectroscopy and its applicability to probe how vibrations modulate charge and energy transfer in a wide range of complex molecular, material, and biological systems.« less
Authors:
 [1] ;  [1] ;  [1] ;  [1]
  1. Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
SC0012450; SC0002190
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 15; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1469485
Alternate Identifier(s):
OSTI ID: 1224223

Courtney, Trevor L., Fox, Zachary W., Slenkamp, Karla M., and Khalil, Munira. Two-dimensional vibrational-electronic spectroscopy. United States: N. p., Web. doi:10.1063/1.4932983.
Courtney, Trevor L., Fox, Zachary W., Slenkamp, Karla M., & Khalil, Munira. Two-dimensional vibrational-electronic spectroscopy. United States. doi:10.1063/1.4932983.
Courtney, Trevor L., Fox, Zachary W., Slenkamp, Karla M., and Khalil, Munira. 2015. "Two-dimensional vibrational-electronic spectroscopy". United States. doi:10.1063/1.4932983. https://www.osti.gov/servlets/purl/1469485.
@article{osti_1469485,
title = {Two-dimensional vibrational-electronic spectroscopy},
author = {Courtney, Trevor L. and Fox, Zachary W. and Slenkamp, Karla M. and Khalil, Munira},
abstractNote = {Two-dimensional vibrational-electronic (2D VE) spectroscopy is a femtosecond Fourier transform (FT) third-order nonlinear technique that creates a link between existing 2D FT spectroscopies in the vibrational and electronic regions of the spectrum. 2D VE spectroscopy enables a direct measurement of infrared (IR) and electronic dipole moment cross terms by utilizing mid-IR pump and optical probe fields that are resonant with vibrational and electronic transitions, respectively, in a sample of interest. We detail this newly developed 2D VE spectroscopy experiment and outline the information contained in a 2D VE spectrum. We then use this technique and its single-pump counterpart (1D VE) to probe the vibrational-electronic couplings between high frequency cyanide stretching vibrations (νCN) and either a ligand-to-metal charge transfer transition ([FeIII(CN)6]3- dissolved in formamide) or a metal-to-metal charge transfer (MMCT) transition ([(CN)5FeIICNRuIII(NH3)5]- dissolved in formamide). The 2D VE spectra of both molecules reveal peaks resulting from coupled high- and low-frequency vibrational modes to the charge transfer transition. The time-evolving amplitudes and positions of the peaks in the 2D VE spectra report on coherent and incoherent vibrational energy transfer dynamics among the coupled vibrational modes and the charge transfer transition. The selectivity of 2D VE spectroscopy to vibronic processes is evidenced from the selective coupling of specific νCN modes to the MMCT transition in the mixed valence complex. The lineshapes in 2D VE spectra report on the correlation of the frequency fluctuations between the coupled vibrational and electronic frequencies in the mixed valence complex which has a time scale of 1 ps. Lastly, the details and results of this study confirm the versatility of 2D VE spectroscopy and its applicability to probe how vibrations modulate charge and energy transfer in a wide range of complex molecular, material, and biological systems.},
doi = {10.1063/1.4932983},
journal = {Journal of Chemical Physics},
number = 15,
volume = 143,
place = {United States},
year = {2015},
month = {10}
}

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