Coherent multidimensional optical spectra measured using incoherent light

Four-wave mixing measurements can reveal spectral and dynamics information that is hidden in linear spectra by the interactions among light-absorbing molecules and with their environment. Coherent multidimensional optical spectroscopy is an important variant of four-wave mixing because it resolves a map of interactions and correlations between absorption bands. Previous coherent multidimensional optical spectroscopy measurements have used femtosecond pulses with great success, and it may seem that femtosecond pulses are necessary for such measurements. Here we present coherent two-dimensional electronic spectra measured using incoherent light. The spectra of model molecular systems using broadband spectrally incoherent light are similar but not identical to those expected from measurements using femtosecond pulses. Specifically, the spectra show particular sensitivity to long-lived intermediates such as photoisomers. The results will motivate the design of similar experiments in spectral ranges where femtosecond pulses are difficult to produce.

[1]  M. Shapiro,et al.  Molecular response in one-photon absorption via natural thermal light vs. pulsed laser excitation , 2011, Proceedings of the National Academy of Sciences.

[2]  J. Ogilvie,et al.  Effects of chirp on two-dimensional Fourier transform electronic spectra. , 2010, Optics express.

[3]  Masahiro Matsuoka,et al.  Ultrafast pump–probe measurement using intensity correlation of incoherent light , 1986 .

[4]  Daniel B. Turner,et al.  Electronic coherence lineshapes reveal hidden excitonic correlations in photosynthetic light harvesting. , 2012, Nature chemistry.

[5]  Jennifer P Ogilvie,et al.  Probing Photosynthetic Energy and Charge Transfer with Two-Dimensional Electronic Spectroscopy. , 2012, The journal of physical chemistry letters.

[6]  Gregory D. Scholes,et al.  Coherently wired light-harvesting in photosynthetic marine algae at ambient temperature , 2010, Nature.

[7]  M T Do,et al.  Noninterferometric two-dimensional fourier-transform spectroscopy of multilevel systems. , 2008, Physical review letters.

[8]  Y. Avlasevich,et al.  Weakly chirped pulses in frequency resolved coherent spectroscopy. , 2010, The Journal of chemical physics.

[9]  Norio Morita,et al.  Ultrahigh-time-resolution coherent transient spectroscopy with incoherent light , 1984 .

[10]  J. Barber,et al.  Two-Dimensional Electronic Spectroscopy Reveals Ultrafast Downhill Energy Transfer in Photosystem I Trimers of the Cyanobacterium Thermosynechococcus elongatus. , 2012, The journal of physical chemistry letters.

[11]  David M. Jonas,et al.  TWO-DIMENSIONAL ELECTRONIC SPECTROSCOPY , 1998 .

[12]  Daniel B. Turner,et al.  Two-Quantum 2D FT Electronic Spectroscopy of Biexcitons in GaAs Quantum Wells , 2009, Science.

[13]  T. Gillbro,et al.  Viscosity-dependent isomerization yields of some cyanine dyes. A picosecond laser spectroscopy study , 1982 .

[14]  Graham R. Fleming,et al.  Two-dimensional spectroscopy of electronic couplings in photosynthesis , 2005, Nature.

[15]  Steven T. Cundiff,et al.  Optical two-dimensional Fourier transform spectroscopy of semiconductors , 2005 .

[16]  M. Zanni,et al.  Vibrational dynamics of ions in glass from fifth-order two-dimensional infrared spectroscopy. , 2005, Physical review letters.

[17]  Y. H. Meyer,et al.  Transient absorption of symmetrical carbocyanines , 1998 .

[18]  Lena A. Yurs,et al.  Multiply Resonant Coherent Multidimensional Spectroscopy: Implications for Materials Science , 2010 .

[19]  Graham R. Fleming,et al.  Chemical applications of ultrafast spectroscopy , 1986 .

[20]  A. Taylor,et al.  The absorption characteristics and recovery dynamics of the tricarbocyanine dye DTP , 1991 .

[21]  R. Hochstrasser,et al.  Two-dimensional spectroscopy at infrared and optical frequencies , 2007, Proceedings of the National Academy of Sciences.

[22]  T. Mančal,et al.  Exciton dynamics in photosynthetic complexes: excitation by coherent and incoherent light , 2010, 1002.0954.

[23]  G. Bodenhausen,et al.  Principles of nuclear magnetic resonance in one and two dimensions , 1987 .

[24]  Raymond J. Beach,et al.  Incoherent photon echoes , 1984 .

[25]  Bernhard Blümich,et al.  White noise nonlinear system analysis in nuclear magnetic resonance spectroscopy , 1987 .

[26]  Shaul Mukamel,et al.  Coherent ultrafast core-hole correlation spectroscopy: x-ray analogues of multidimensional NMR. , 2007, Physical review letters.

[27]  T. Mančal,et al.  Evidence for wavelike energy transfer through quantum coherence in photosynthetic systems , 2007, Nature.

[28]  M. Shapiro.  Quantum dynamics experienced by a single molecular eigenstate excited by incoherent light. , 2013, Physical review letters.

[29]  Masahiro Fujiwara,et al.  Accumulated photon echoes with incoherent light in Nd 3+ -doped silicate glass , 1984 .

[30]  J. Sperling,et al.  High frequency vibrational modulations in two-dimensional electronic spectra and their resemblance to electronic coherence signatures. , 2011, The journal of physical chemistry. B.

[31]  G. Duxbury.  Fourier transform infrared spectroscopy , 1978, Nature.

[32]  Juan P. Villabona-Monsalve,et al.  Dynamics of the higher lying excited states of cyanine dyes. An ultrafast fluorescence study. , 2013, The journal of physical chemistry. B.

[33]  G. Scholes,et al.  Coherent Energy Transfer under Incoherent Light Conditions. , 2012, The journal of physical chemistry letters.

[34]  R. Hochstrasser,et al.  STRUCTURE OF THE AMIDE I BAND OF PEPTIDES MEASURED BY FEMTOSECOND NONLINEAR-INFRARED SPECTROSCOPY , 1998 .

[35]  Gregory D. Scholes,et al.  Comparison of Electronic and Vibrational Coherence Measured by Two-Dimensional Electronic Spectroscopy , 2011 .

[36]  M. Cho.  Two-Dimensional Optical Spectroscopy , 2009 .

[37]  Justin R Caram,et al.  Long-lived quantum coherence in photosynthetic complexes at physiological temperature , 2010, Proceedings of the National Academy of Sciences.

[38]  Daniel B. Turner,et al.  Two-dimensional electronic spectroscopy using incoherent light: theoretical analysis. , 2012, The journal of physical chemistry. A.

[39]  Daniel B. Turner,et al.  Coherent measurements of high-order electronic correlations in quantum wells , 2010, Nature.

[40]  N. Demirdöven,et al.  Correlated vibrational dynamics revealed by two-dimensional infrared spectroscopy. , 2002, Physical review letters.

[41]  Peifang Tian,et al.  Femtosecond Phase-Coherent Two-Dimensional Spectroscopy , 2003, Science.

[42]  V. Prokhorenko,et al.  Coherently-controlled two-dimensional photon echo electronic spectroscopy. , 2009, Optics express.

[43]  A. Bristow,et al.  Optical two-dimensional fourier transform spectroscopy of semiconductor quantum wells. , 2009, Accounts of chemical research.

[44]  B. K. Mishra,et al.  Cyanines during the 1990s: A Review. , 2000, Chemical reviews.

[45]  K. Kreher.  Ultrafast Spectroscopy of Semiconductors and Semiconductor Nanostructures , 1997 .

[46]  Daniel B. Turner,et al.  Quantitative investigations of quantum coherence for a light-harvesting protein at conditions simulating photosynthesis. , 2012, Physical chemistry chemical physics : PCCP.

[47]  O. Faix,et al.  Fourier Transform Infrared Spectroscopy , 1992 .

[48]  Galan Moody,et al.  Unraveling quantum pathways using optical 3D Fourier-transform spectroscopy , 2013, Nature Communications.

[49]  V. Sundström,et al.  Viscosity dependent radiationless relaxation rate of cyanine dyes. A picosecond laser spectroscopy study , 1981 .

[50]  Martin T. Zanni,et al.  Concepts and Methods of 2D Infrared Spectroscopy , 2011 .

[51]  Robert C. Wolpert,et al.  A Review of the , 1985 .

[52]  Andrew M. Moran,et al.  Nonlinear optical signatures of ultraviolet light-induced ring opening in α-terpinene , 2013 .

[53]  S. Mukamel.  Principles of Nonlinear Optical Spectroscopy , 1995 .

[54]  Joseph E. Ford,et al.  Reactive self-tracking solar concentrators: concept, design, and initial materials characterization. , 2012, Applied optics.

[55]  D. Egorova.  Detection of electronic and vibrational coherences in molecular systems by 2D electronic photon echo spectroscopy , 2008 .

[56]  Graham R Fleming,et al.  Dynamics of light harvesting in photosynthesis. , 2009, Annual review of physical chemistry.

[57]  G. Ripandelli,et al.  Optical coherence tomography. , 1998, Seminars in ophthalmology.