Femtosecond broadband stimulated Raman spectroscopy: Apparatus and methods.

The laser, detection system, and methods that enable femtosecond broadband stimulated Raman spectroscopy (FSRS) are presented in detail. FSRS is a unique tool for obtaining high time resolution (<100 fs) vibrational spectra with an instrument response limited frequency resolution of <10 cm(-1). A titanium:Sapphire-based laser system produces the three different pulses needed for FSRS: (1) A femtosecond visible actinic pump that initiates the photochemistry, (2) a narrow bandwidth picosecond Raman pump that provides the energy reservoir for amplification of the probe, and (3) a femtosecond continuum probe that is amplified at Raman resonances shifted from the Raman pump. The dependence of the stimulated Raman signal on experimental parameters is explored, demonstrating the expected exponential increase in Raman intensity with concentration, pathlength, and Raman pump power. Raman spectra collected under different electronic resonance conditions using highly fluorescent samples highlight the fluorescence rejection capabilities of FSRS. Data are also presented illustrating our ability: (i) To obtain spectra when there is a large transient absorption change by using a shifted excitation difference technique and (ii) to obtain high time resolution vibrational spectra of transient electronic states.

[1]  R. Mathies,et al.  Theory of femtosecond stimulated Raman spectroscopy. , 2004, The Journal of chemical physics.

[2]  R. Mathies,et al.  Femtosecond Time-Resolved Stimulated Raman Spectroscopy of the S2(1Bu+) Excited State of β-Carotene , 2004 .

[3]  R. Mathies,et al.  Vibrational structure of the S2 (1Bu) excited state of diphenyloctatetraene observed by femtosecond stimulated Raman spectroscopy , 2003 .

[4]  Richard A Mathies,et al.  Femtosecond Broadband Stimulated Raman: A New Approach for High-Performance Vibrational Spectroscopy , 2003, Applied spectroscopy.

[5]  R. Mathies,et al.  Flowing liquid sample jet for resonance Raman and ultrafast optical spectroscopy , 2003 .

[6]  R. Mathies,et al.  Femtosecond Time-Resolved Stimulated Raman Spectroscopy: Application to the Ultrafast Internal Conversion in β-Carotene† , 2003 .

[7]  H. Hashimoto,et al.  Ultrafast relaxation kinetics of excited states in a series of mini- and macro-β-carotenes , 2003 .

[8]  P. Champion,et al.  Resonance Raman investigations of cytochrome c conformational change upon interaction with the membranes of intact and Ca2+-exposed mitochondria. , 2003, Biochemistry.

[9]  S. Silvestri,et al.  Ultrafast optical parametric amplifiers , 2003 .

[10]  R. Mathies,et al.  Anti-stokes Raman study of vibrational cooling dynamics in the primary photochemistry of rhodopsin. , 2002, The journal of physical chemistry. A.

[11]  Fritz S. Allen,et al.  Automated Fluorescence Rejection Using Shifted Excitation Raman Difference Spectroscopy , 2002 .

[12]  R. Mathies,et al.  Vibrational Relaxation in β-Carotene Probed by Picosecond Stokes and Anti-Stokes Resonance Raman Spectroscopy , 2002 .

[13]  Jianping Zhang,et al.  Internal-conversion and radiative-transition processes among the 1Bu+, 1Bu− and 2Ag− states of all-trans-neurosporene as revealed by subpicosecond time-resolved Raman spectroscopy , 2002 .

[14]  Chunyan He,et al.  Probing M-Branch Electron Transfer and Cofactor Environment in the Bacterial Photosynthetic Reaction Center by Addition of a Hydrogen Bond to the M-Side Bacteriopheophytin , 2002 .

[15]  Robert Eugene Blankenship.  Molecular mechanisms of photosynthesis , 2002 .

[16]  L. Kiger,et al.  Heme photolysis occurs by ultrafast excited state metal-to-ring charge transfer. , 2001, Biophysical journal.

[17]  R. Mathies,et al.  Resonance Raman Structural Evidence that the Cis-to-Trans Isomerization in Rhodopsin Occurs in Femtoseconds. , 2001, The journal of physical chemistry. B.

[18]  M. Kubo,et al.  Ultrafast photoisomerization in DCM dye observed by new femtosecond Raman spectroscopy , 2000 .

[19]  Ingo Fischer,et al.  Transient stimulated Raman scattering in gas mixtures. , 1999, Optics letters.

[20]  K. Midorikawa,et al.  High-energy conversion efficiency of transient stimulated Raman scattering in methane pumped by the fundamental of a femtosecond Ti:sapphire laser. , 1999, Optics letters.

[21]  R. Mathies,et al.  Picosecond time-resolved Raman system for studying photochemical reaction dynamics: application to the primary events in vision , 1999 .

[22]  Robert R. Alfano,et al.  Femtosecond laser pulses : principles and experiments , 1999 .

[23]  M. El-Sayed,et al.  Primary Step in Bacteriorhodopsin Photosynthesis: Bond Stretch Rather than Angle Twist of Its Retinal Excited-State Structure , 1998 .

[24]  P. Reid,et al.  Geminate recombination and vibrational relaxation dynamics of aqueous chlorine dioxide: A time-resolved resonance Raman study , 1998 .

[25]  D. F. Bocian,et al.  Qy-Excitation Resonance Raman Spectra of Chlorophyll a and Related Complexes. Normal Mode Characteristics of the Low-Frequency Vibrations , 1997 .

[26]  Ch. J. Bordé,et al.  Line-shape studies in high-resolution stimulated resonance Raman spectroscopy and application to accurate determinations of hyperfine splittings in I 2 , 1996 .

[27]  S. Yamaguchi,et al.  Convenient Method of Measuring the Chirp Structure of Femtosecond White-Light Continuum Pulses , 1995 .

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

[29]  R. Mathies,et al.  Determination of Pericyclic Photochemical Reaction Dynamics with Resonance Raman Spectroscopy , 1994 .

[30]  Kobayashi,et al.  Femtosecond time-resolved resonance Raman gain spectroscopy in polydiacetylene. , 1994, Physical review. B, Condensed matter.

[31]  Y. Ozaki,et al.  Spectroscopic studies of thiatri-, penta- and heptamethine cyanine dyes II. Infrared and resonance Raman spectra of thiatri-, penta- and heptamethine cyanine dyes , 1992 .

[32]  M M Murnane,et al.  17-fs pulses from a self-mode-locked Ti:sapphire laser. , 1992, Optics letters.

[33]  Richard A. Mathies,et al.  Effective Rejection of Fluorescence Interference in Raman Spectroscopy Using a Shifted Excitation Difference Technique , 1992 .

[34]  J. Reintjes,et al.  Transient stimulated Raman amplification in hydrogen , 1988 .

[35]  Oscar E. Martínez,et al.  3000 times grating compressor with positive group velocity dispersion: Application to fiber compensation in 1.3-1.6 µm region , 1987 .

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

[37]  M. Levenson.  The principles of nonlinear optics , 1985, IEEE Journal of Quantum Electronics.

[38]  P. Hildebrandt,et al.  Surface-enhanced resonance Raman spectroscopy of Rhodamine 6G adsorbed on colloidal silver , 1984 .

[39]  J. Gordon,et al.  Negative dispersion using pairs of prisms. , 1984, Optics letters.

[40]  R. Clark,et al.  Advances in Infrared and Raman Spectroscopy , 1982 .

[41]  C. Bethea,et al.  Ultrahigh sensitivity stimulated Raman gain spectroscopy , 1980 .

[42]  R. Mathies,et al.  Raman spectroscopy with intensified vidicon detectors: A study of intact bovine lens proteins , 1978 .

[43]  W. Kaiser,et al.  Vibrational dynamics of liquids and solids investigated by picosecond light pulses , 1978 .

[44]  A. Owyoung,et al.  Coherent Raman gain spectroscopy using CW laser sources , 1978 .

[45]  G. Frushour,et al.  Advances in Infrared and Raman Spectroscopy , 1975 .

[46]  C. S. Wang,et al.  THEORY OF STOKES PULSE SHAPES IN TRANSIENT STIMULATED RAMAN SCATTERING. , 1970 .