2D IR spectroscopy of the C-D stretching vibration of the deuterated formic acid dimer.

We report transient grating and 2D IR spectra of the C-D stretching vibration of deuterated formic acid dimer. The C-D stretching transition is perturbed by an accidental Fermi resonance interaction that gives rise to a second transition. The transient grating results show that the population lifetime of these states, which are in rapid equilibrium, is 11 ps. 2D IR spectroscopy reveals the energies of the eigenstates in the regions of one quantum and two quanta of C-D stretching excitation. Using these eigenstate energies, we construct a simplified model for the zeroth-order states that we then use to simulate the 2D IR spectrum. The results of this simulation suggest that the model captures the essential features of the vibrational spectroscopy in the region of the C-D stretching transition and compares well with previous gas-phase spectroscopy of the C-D stretch of deuterated formic acid dimer.

[1]  Direct observation of structural heterogeneity in a beta-sheet. , 2009, Journal of the American Chemical Society.

[2]  R. Hochstrasser,et al.  Vibrational dynamics of N-H, C-D, and C=O modes in formamide. , 2006, The Journal of chemical physics.

[3]  M. Thielges,et al.  C-D modes of deuterated side chain of leucine as structural reporters via dual-frequency two-dimensional infrared spectroscopy. , 2009, The journal of physical chemistry. B.

[4]  Graham R. Fleming,et al.  Third-order nonlinear time domain probes of solvation dynamics , 1996 .

[5]  J. Eaves,et al.  Electric field fluctuations drive vibrational dephasing in water. , 2005, The journal of physical chemistry. A.

[6]  R. Hochstrasser,et al.  Two-Dimensional Infrared Spectra of the 13C18O Isotopomers of Alanine Residues in an α-Helix , 2005 .

[7]  Jigar N. Bandaria,et al.  Vibrational relaxation of C-D stretching vibrations in CDCl3, CDBr3, and CDI3. , 2006, The Journal of chemical physics.

[8]  Jigar N. Bandaria,et al.  Exploring the molecular origins of protein dynamics in the active site of human carbonic anhydrase II. , 2009, The journal of physical chemistry. B.

[9]  D. Raleigh,et al.  Two-dimensional IR spectroscopy and isotope labeling defines the pathway of amyloid formation with residue-specific resolution , 2009, Proceedings of the National Academy of Sciences.

[10]  J. Loparo,et al.  Local hydrogen bonding dynamics and collective reorganization in water: ultrafast infrared spectroscopy of HOD/D(2)O. , 2005, The Journal of chemical physics.

[11]  J. Asbury,et al.  Hydrogen Bond Networks: Structure and Evolution after Hydrogen Bond Breaking † , 2004 .

[12]  R. Hochstrasser,et al.  Non-Markovian Dynamics of the Vibrations of Ions in Water from Femtosecond Infrared Three-Pulse Photon Echoes , 1998 .

[13]  D. Raleigh,et al.  Strategies for extracting structural information from 2D IR spectroscopy of amyloid: application to islet amyloid polypeptide. , 2009, The journal of physical chemistry. B.

[14]  Andrei Tokmakoff,et al.  Coherent 2D IR Spectroscopy: Molecular Structure and Dynamics in Solution , 2003 .

[15]  S. Corcelli,et al.  Carbon-deuterium vibrational probes of peptide conformation: alanine dipeptide and glycine dipeptide. , 2009, The Journal of chemical physics.

[16]  S. Boxer,et al.  Vibrational Stark effects calibrate the sensitivity of vibrational probes for electric fields in proteins. , 2003, Biochemistry.

[17]  J. Skinner,et al.  Dynamics of water probed with vibrational echo correlation spectroscopy. , 2004, The Journal of chemical physics.

[18]  J. Skinner,et al.  Water Dynamics: Vibrational Echo Correlation Spectroscopy and Comparison to Molecular Dynamics Simulations , 2004 .

[19]  Michael L. Hause,et al.  Vibrational action spectroscopy of the C-H and C-D stretches in partially deuterated formic acid dimer. , 2008, The Journal of chemical physics.

[20]  M. Fayer.  Dynamics of Molecules in Condensed Phases: Picosecond Holographic Grating Experiments , 1982 .

[21]  R. Hochstrasser,et al.  Vibrational coupling, isotopic editing, and beta-sheet structure in a membrane-bound polypeptide. , 2004, Journal of the American Chemical Society.

[22]  Louise E. Sinks,et al.  Coupling between C–D and CO motions using dual-frequency 2D IR photon echo spectroscopy , 2006 .

[23]  G. Seifert,et al.  Time-resolved observation of intermolecular vibrational energy transfer in liquid bromoform , 2000 .

[24]  H. Lessing,et al.  Theory of laser-induced amplitude and phase gratings including photoselection, orientational relaxation and population kinetics , 1979 .

[25]  Michael D. Fayer,et al.  Polarization selective spectroscopy experiments: methodology and pitfalls , 2005 .

[26]  Ilya J. Finkelstein,et al.  Probing dynamics of complex molecular systems with ultrafast 2D IR vibrational echo spectroscopy. , 2007, Physical chemistry chemical physics : PCCP.

[27]  Floyd E Romesberg,et al.  Efforts toward developing probes of protein dynamics: vibrational dephasing and relaxation of carbon-deuterium stretching modes in deuterated leucine. , 2009, The journal of physical chemistry. B.

[28]  R. Jimenez,et al.  Direct observation of protein vibrations by selective incorporation of spectroscopically observable carbon-deuterium bonds in cytochrome c. , 2001, Journal of the American Chemical Society.

[29]  D. Case,et al.  Carbon-deuterium bonds as probes of dihydrofolate reductase. , 2008, Journal of the American Chemical Society.

[30]  R. Hochstrasser,et al.  Determination of the vibrational energy relaxation time of the azide ion in protic solvents by two-color transient infrared spectroscopy , 1991 .

[31]  F. Romesberg,et al.  Infrared Line Shape of an α-Carbon Deuterium-Labeled Amino Acid , 2006 .

[32]  J. D. de Pablo,et al.  2D IR line shapes probe ovispirin peptide conformation and depth in lipid bilayers. , 2010, Journal of the American Chemical Society.

[33]  D. Kurochkin,et al.  C–D Modes as structural reporters via dual-frequency 2DIR spectroscopy , 2007 .

[34]  Jigar N. Bandaria,et al.  Relaxation and anharmonic couplings of the O-H stretching vibration of asymmetric strongly hydrogen-bonded complexes. , 2007, The Journal of chemical physics.

[35]  C. Toniolo,et al.  Vibrational energy transport in peptide helices after excitation of C-D modes in Leu-d10. , 2009, The journal of physical chemistry. B.

[36]  J. Skinner,et al.  Water dynamics: dependence on local structure probed with vibrational echo correlation spectroscopy , 2004 .

[37]  Junrong Zheng,et al.  Ultrafast Dynamics of Solute-Solvent Complexation Observed at Thermal Equilibrium in Real Time , 2005, Science.

[38]  S. Corcelli,et al.  Carbon-deuterium vibrational probes of amino acid protonation state. , 2009, The journal of physical chemistry. B.

[39]  J. Asbury,et al.  Vibrational echo correlation spectroscopy probes of hydrogen bond dynamics in water and methanol. , 2004, Journal of luminescence.