Abstract

Multidimensional infrared spectroscopy is a robust tool for studying the structural dynamics of molecules. In particular, two-dimensional infrared (2DIR) spectroscopy can reveal vibrational coupling among the internal modes of molecules, uncovering the transient structure of complex systems. While spectroscopically very powerful, current experimental techniques are time consuming to perform, requiring ~ 106 laser shots for a single 2DIR spectrum. In this work, we demonstrate a new technique that can acquire a full 2DIR correlation spectrum using a single ultrafast laser pulse. This apparatus will allow 2DIR spectroscopy to be extended to systems that were unattainable with previous technology,including, irreversible chemical reactions, rapid flow experiments, or with low repetition rate laser systems.

© 2007 Optical Society of America

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    [CrossRef]
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    [CrossRef]
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    [CrossRef]
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    [CrossRef] [PubMed]
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    [CrossRef] [PubMed]
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    [CrossRef]
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    [CrossRef] [PubMed]
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    [CrossRef]
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    [CrossRef]
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2006

2005

K.J. Kubarych, M. Joffre, A. Moore, N. Belabas, and D.M. Jonas "Mid-infrared electric field characterization using a visible charge-coupled-device-based spectrometer," Opt. Lett. 301228 (2005).
[CrossRef] [PubMed]

M. F. DeCamp and A. Tokmakoff. "Upconversion multichannel Infrared spectrometer," Opt. Lett. 301818 (2005).
[CrossRef] [PubMed]

T. Brixner, J. Stenger, H. M. Vaswani, M. Cho, R.E. Blankenship, and G.R. Fleming, "Two-dimensional spectroscopy of electronic couplings in photosynthesis," Nature 434625 (2005).
[CrossRef] [PubMed]

C.N. Borca, T. Zhang, X. Li, and S.T. Cundiff, "Optical two-dimensional Fourier transform spectrscopy of semiconductors," Chem. Phys. Lett.,  416311 (2005).
[CrossRef]

2004

V. Cervetto, J. Helbing, J. Bredenbeck, and P. Hamm, "Double-resonance versus pulsed Fourier transform two-dimensional infrared spectroscopy: An experimental and theoretical comparison," J. Chem. Phys.,  1215935 (2004).
[CrossRef] [PubMed]

2003

J.B. Asbury, T. Steinel, and M.D. Fayer, "Using ultrafast Infraed multidimensional correlation spectroscopy to aid in vibrational spectral peak assignments," Chem. Phys. Lett. 381139 (2003).
[CrossRef]

M. Khalil, N. Demirdoven, and A. Tokmakoff, "Coherent 2D IR spectoscopy: Molecular Structure and Dynamics in Solution," J. Phys. Chem. A 1075258 (2003).
[CrossRef]

2002

J.D Hybl, A. Yu, D.A. Farrow, D.M. and Jonas, D. M.,"Polar solvation dynamics in the femtosecond evolution of two-dimensional Fourier transform spectra," J. Phys. Chem. A 1067651 (2002).
[CrossRef]

2000

A. Tokmakoff, "Two-dimensional line shapes derived from coherent third-order nonlinear spectroscopy," J. Phys. Chem. A, 1044247 (2000).
[CrossRef]

1998

P. Hamm, M. Lim, and R.M. Hochstrasser, "The structure of the amide I band of peptides measured by femtosecond nonlinear IR spectroscopy," J. Phys. Chem. B,  1026123 (1998).
[CrossRef]

1996

1994

1989

Asbury, J.B.

J.B. Asbury, T. Steinel, and M.D. Fayer, "Using ultrafast Infraed multidimensional correlation spectroscopy to aid in vibrational spectral peak assignments," Chem. Phys. Lett. 381139 (2003).
[CrossRef]

Belabas, N.

Blankenship, R.E.

T. Brixner, J. Stenger, H. M. Vaswani, M. Cho, R.E. Blankenship, and G.R. Fleming, "Two-dimensional spectroscopy of electronic couplings in photosynthesis," Nature 434625 (2005).
[CrossRef] [PubMed]

Borca, C.N.

C.N. Borca, T. Zhang, X. Li, and S.T. Cundiff, "Optical two-dimensional Fourier transform spectrscopy of semiconductors," Chem. Phys. Lett.,  416311 (2005).
[CrossRef]

Bredenbeck, J.

V. Cervetto, J. Helbing, J. Bredenbeck, and P. Hamm, "Double-resonance versus pulsed Fourier transform two-dimensional infrared spectroscopy: An experimental and theoretical comparison," J. Chem. Phys.,  1215935 (2004).
[CrossRef] [PubMed]

Brixner, T.

T. Brixner, J. Stenger, H. M. Vaswani, M. Cho, R.E. Blankenship, and G.R. Fleming, "Two-dimensional spectroscopy of electronic couplings in photosynthesis," Nature 434625 (2005).
[CrossRef] [PubMed]

Cervetto, V.

V. Cervetto, J. Helbing, J. Bredenbeck, and P. Hamm, "Double-resonance versus pulsed Fourier transform two-dimensional infrared spectroscopy: An experimental and theoretical comparison," J. Chem. Phys.,  1215935 (2004).
[CrossRef] [PubMed]

Cho, M.

T. Brixner, J. Stenger, H. M. Vaswani, M. Cho, R.E. Blankenship, and G.R. Fleming, "Two-dimensional spectroscopy of electronic couplings in photosynthesis," Nature 434625 (2005).
[CrossRef] [PubMed]

Cundiff, S.T.

C.N. Borca, T. Zhang, X. Li, and S.T. Cundiff, "Optical two-dimensional Fourier transform spectrscopy of semiconductors," Chem. Phys. Lett.,  416311 (2005).
[CrossRef]

DeCamp, M. F.

Demirdoven, N.

M. Khalil, N. Demirdoven, and A. Tokmakoff, "Coherent 2D IR spectoscopy: Molecular Structure and Dynamics in Solution," J. Phys. Chem. A 1075258 (2003).
[CrossRef]

Dougherty, T.P.

Farrow, D.A.

J.D Hybl, A. Yu, D.A. Farrow, D.M. and Jonas, D. M.,"Polar solvation dynamics in the femtosecond evolution of two-dimensional Fourier transform spectra," J. Phys. Chem. A 1067651 (2002).
[CrossRef]

Fayer, M.D.

J.B. Asbury, T. Steinel, and M.D. Fayer, "Using ultrafast Infraed multidimensional correlation spectroscopy to aid in vibrational spectral peak assignments," Chem. Phys. Lett. 381139 (2003).
[CrossRef]

Fleming, G.R.

T. Brixner, J. Stenger, H. M. Vaswani, M. Cho, R.E. Blankenship, and G.R. Fleming, "Two-dimensional spectroscopy of electronic couplings in photosynthesis," Nature 434625 (2005).
[CrossRef] [PubMed]

Hamm, P.

V. Cervetto, J. Helbing, J. Bredenbeck, and P. Hamm, "Double-resonance versus pulsed Fourier transform two-dimensional infrared spectroscopy: An experimental and theoretical comparison," J. Chem. Phys.,  1215935 (2004).
[CrossRef] [PubMed]

P. Hamm, M. Lim, and R.M. Hochstrasser, "The structure of the amide I band of peptides measured by femtosecond nonlinear IR spectroscopy," J. Phys. Chem. B,  1026123 (1998).
[CrossRef]

Heilweil, E.J.

Helbing, J.

V. Cervetto, J. Helbing, J. Bredenbeck, and P. Hamm, "Double-resonance versus pulsed Fourier transform two-dimensional infrared spectroscopy: An experimental and theoretical comparison," J. Chem. Phys.,  1215935 (2004).
[CrossRef] [PubMed]

Hochstrasser, R.M.

P. Hamm, M. Lim, and R.M. Hochstrasser, "The structure of the amide I band of peptides measured by femtosecond nonlinear IR spectroscopy," J. Phys. Chem. B,  1026123 (1998).
[CrossRef]

Hybl, J.D

J.D Hybl, A. Yu, D.A. Farrow, D.M. and Jonas, D. M.,"Polar solvation dynamics in the femtosecond evolution of two-dimensional Fourier transform spectra," J. Phys. Chem. A 1067651 (2002).
[CrossRef]

Joffre, M.

Jonas, D.M.

Khalil, M.

M. Khalil, N. Demirdoven, and A. Tokmakoff, "Coherent 2D IR spectoscopy: Molecular Structure and Dynamics in Solution," J. Phys. Chem. A 1075258 (2003).
[CrossRef]

Kubarych, K.J.

Lepetit, L.

Li, X.

C.N. Borca, T. Zhang, X. Li, and S.T. Cundiff, "Optical two-dimensional Fourier transform spectrscopy of semiconductors," Chem. Phys. Lett.,  416311 (2005).
[CrossRef]

Lim, M.

P. Hamm, M. Lim, and R.M. Hochstrasser, "The structure of the amide I band of peptides measured by femtosecond nonlinear IR spectroscopy," J. Phys. Chem. B,  1026123 (1998).
[CrossRef]

Moore, A.

Steinel, T.

J.B. Asbury, T. Steinel, and M.D. Fayer, "Using ultrafast Infraed multidimensional correlation spectroscopy to aid in vibrational spectral peak assignments," Chem. Phys. Lett. 381139 (2003).
[CrossRef]

Stenger, J.

T. Brixner, J. Stenger, H. M. Vaswani, M. Cho, R.E. Blankenship, and G.R. Fleming, "Two-dimensional spectroscopy of electronic couplings in photosynthesis," Nature 434625 (2005).
[CrossRef] [PubMed]

Tokmakoff, A.

M. F. DeCamp. and A. Tokmakoff, "Single-shot two-dimensional spectrometer," Opt. Lett. 31113 (2006).
[CrossRef] [PubMed]

M. F. DeCamp and A. Tokmakoff. "Upconversion multichannel Infrared spectrometer," Opt. Lett. 301818 (2005).
[CrossRef] [PubMed]

M. Khalil, N. Demirdoven, and A. Tokmakoff, "Coherent 2D IR spectoscopy: Molecular Structure and Dynamics in Solution," J. Phys. Chem. A 1075258 (2003).
[CrossRef]

A. Tokmakoff, "Two-dimensional line shapes derived from coherent third-order nonlinear spectroscopy," J. Phys. Chem. A, 1044247 (2000).
[CrossRef]

Vaswani, H. M.

T. Brixner, J. Stenger, H. M. Vaswani, M. Cho, R.E. Blankenship, and G.R. Fleming, "Two-dimensional spectroscopy of electronic couplings in photosynthesis," Nature 434625 (2005).
[CrossRef] [PubMed]

Yu, A.

J.D Hybl, A. Yu, D.A. Farrow, D.M. and Jonas, D. M.,"Polar solvation dynamics in the femtosecond evolution of two-dimensional Fourier transform spectra," J. Phys. Chem. A 1067651 (2002).
[CrossRef]

Zhang, T.

C.N. Borca, T. Zhang, X. Li, and S.T. Cundiff, "Optical two-dimensional Fourier transform spectrscopy of semiconductors," Chem. Phys. Lett.,  416311 (2005).
[CrossRef]

Chem. Phys. Lett.

J.B. Asbury, T. Steinel, and M.D. Fayer, "Using ultrafast Infraed multidimensional correlation spectroscopy to aid in vibrational spectral peak assignments," Chem. Phys. Lett. 381139 (2003).
[CrossRef]

C.N. Borca, T. Zhang, X. Li, and S.T. Cundiff, "Optical two-dimensional Fourier transform spectrscopy of semiconductors," Chem. Phys. Lett.,  416311 (2005).
[CrossRef]

J. Chem. Phys.

V. Cervetto, J. Helbing, J. Bredenbeck, and P. Hamm, "Double-resonance versus pulsed Fourier transform two-dimensional infrared spectroscopy: An experimental and theoretical comparison," J. Chem. Phys.,  1215935 (2004).
[CrossRef] [PubMed]

J. Phys. Chem. A

M. Khalil, N. Demirdoven, and A. Tokmakoff, "Coherent 2D IR spectoscopy: Molecular Structure and Dynamics in Solution," J. Phys. Chem. A 1075258 (2003).
[CrossRef]

A. Tokmakoff, "Two-dimensional line shapes derived from coherent third-order nonlinear spectroscopy," J. Phys. Chem. A, 1044247 (2000).
[CrossRef]

J.D Hybl, A. Yu, D.A. Farrow, D.M. and Jonas, D. M.,"Polar solvation dynamics in the femtosecond evolution of two-dimensional Fourier transform spectra," J. Phys. Chem. A 1067651 (2002).
[CrossRef]

J. Phys. Chem. B

P. Hamm, M. Lim, and R.M. Hochstrasser, "The structure of the amide I band of peptides measured by femtosecond nonlinear IR spectroscopy," J. Phys. Chem. B,  1026123 (1998).
[CrossRef]

Nature

T. Brixner, J. Stenger, H. M. Vaswani, M. Cho, R.E. Blankenship, and G.R. Fleming, "Two-dimensional spectroscopy of electronic couplings in photosynthesis," Nature 434625 (2005).
[CrossRef] [PubMed]

Opt. Lett.

Other

Preliminary experiments have indicated that a 100 μm thick piece of MgO:LiNbO3 is partially transparent in the mid-IR spectral regions making upconverion at wavelengths greater than 6 μm possible.

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Figures (4)

Fig. 1.
Fig. 1.

2DIR spectrometer. G is diffraction grating, SL is a spherical focusing mirror, CL is a cylindrical lens, BS is a beamsplitter, and MLN is the upconversion crystal.

Fig. 2.
Fig. 2.

2DIR spectra of WHC in (a) chloroform and (b) hexane. The corresponding FTIR spectra of each system are shown above the 2D spectra. Each spectra was averaged from 105 laser shots.

Fig. 3.
Fig. 3.

2DIR spectra of RDC in hexane acquired by averaging 105 laser shots. Each contour level corresponds to a change in transmission of 0.1mOD.

Fig. 4.
Fig. 4.

Time series of 2DIR difference spectra of WHC in hexane using (a) 1 (b) 16 (c) 256 (d) and 4096 pump-probe pulses.

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