The people involved:
Lukasz Szyc, Ming Yang, Mirabelle Prémont-Schwarz, Jens Dreyer, Erik T. J. Nibbering, Thomas Elsaesser
Former team members:
Jens Stenger, Dorte Madsen, Nils Huse, Peter Hamm, Karsten Heyne, Satoshi Ashihara, Agathe Espagne, Jason. R. Dwyer

Collaboration within Berlin scientific arena: Milena Petkovic,^† Oliver Kühn,^† Gianina Gavrila,º Kai Godehusen,º Christian Weniger,º Philippe Wernet,º Wolfgang Eberhardtº
^†: Through SFB-450 (Teilprojekt C1): Freie Universität Berlin, Institut für Chemie, Physikalische und Theoretische Chemie, Takustrasse 3, D-14195 Berlin, Germany
º: Ultrafast X-Ray Science Group, BESSY, Berlin, Germany

International collaboration: Barry D. Bruner,* Michael L. Cowan,* Darren Kraemer,* Alexander Paarmann,* Jason R. Dwyer,* Brige Chugh,* Maher Harb,* R. J. Dwayne Miller ,* Shaul Mukamel^#
*: Department of Chemistry and Physics, University of Toronto, 80 St. George Street, Toronto, Ontario, Canada, M5S 3H6
^#: Department of Chemistry, University of California at Irvine, Irvine, California, USA

This research project is embedded within the Collaborative Research Center
SFB 450 "Analysis and control of ultrafast photoinduced reactions"

Strategic approach

1. We investigate the structural and dynamical aspects of hydrogen bond networks by determination of the coherent vibrational response of intra- and intermolecular modes that function as probe of these hydrogen bonds. In particular the O-H stretching and bending modes are extremely sensitive to the strength and dynamical fluctuations exerted on the hydrogen bonds, as being caused by the substantial anharmonic couplings of these modes with other fingerprint vibrations and with the low-frequency hydrogen bond modes. This is exemplified by the pronounced frequency red-shift and line broadening of the IR-active vibrational transitions of the O-H stretching modes.

2. We pursue frequency resolved two-colour pump-probe and homodyne and heterodyne detected photon echo spectroscopy in the mid-infrared spectral region. Depending on the technique different characteristic features of hydrogen bonds can be explored.

Our research activities can be categorized into three time periods.

Phase 1 (1999-2002):

1-1 Coherent wavepacket motions in medium-strong intramolecular hydrogen bonds
1-2 Ultrafast dephasing and spectral diffusion of isotopically diluted water

Phase 2 (2002-2006):

2-1 Coherent wavepacket motions in medium-strong intermolecular hydrogen bonds
2-2 Ultrafast dephasing, spectral diffusion and vibrational relaxation of neat liquid water

Phase 3 (2006-201?):

3-1 Vibrational dynamics in hydrated adenine-thymine DNA oligomers, and biomimetic hydrogen-bonded base-pair systems
3-2 Ultrafast response of the oxygen K-edge of neat liquid water upon a temperature jump

Vibrational dynamics in hydrated adenine-thymine DNA oligomers, and biomimetic hydrogen-bonded base-pair systems

The generation of vibrational wave packets is an essential requisite for optical control of nuclear motion and requires the optical preparation of a coherent superposition of several nuclear wave functions. This should be achieved on hydrogen bonded systems in the electronic ground state through coherent excitation of several levels of low-frequency vibrational modes, that modulate the length of the hydrogen bond. We have indicated the potential feasibility of this coherent control scheme by excitation in the mid-infrared of the O-H or O-D stretching vibrational degrees of freedom, onto which the these low-frequency modes couple anharmonically. We show by use of femtosecond mid-infrared pump-probe and four-wave mixing spectroscopies that this anharmonic coupling can be determined in the time domain from which we learn the temporal characteristics (dephasing) of the vibrational wave packets, and the dephasing (T₂) and population (T₁) dynamics of the O-H/O-D stretching vibrations. From these nonlinear spectroscopic experiments we also aim to obtain information on the nature of the hydrogen bond by determination of the underlying direct (O-H/O-D stretch - solvent) and indirect (O-H/O-D stretch - low-frequency mode - solvent) coupling mechanisms that lead to dephasing and relaxation phenomena, the extraordinary characteristics of which also lead to the very specific line shapes of the O-H/O-D stretching modes, as exemplified by the strong red-shift, extreme broadening and peculiar substructures of these bands.

3. Vibrational perspective of hydrogen bonds: typically a strong anharmonic coupling exists between the O-H/O-D stretching and low-frequency modes that modulate the hydrogen bond distance. For this set of coupled oscillators this has the consequence that excitation of the O-H/O-D stretching mode includes excitation of these low-frequency modes, in a similar fashion as electronic excitation of molecules is accompanied by vibrational excitation. Ultrafast excitation of the O-H/O-D stretching mode in the mid-infrared thus leads to coherent wave packet motions of these low-frequency modes.

4. 7-Azaindole forms a cyclic dimer with two identical medium-strong hydrogen bonds in nonpolar solvents. The molecular structure of this dimer has often been regarded as a model case for DNA base pairing.

5. Transient IR spectra measured for 7-azaindole dimer measured in CCl4 for different pulse delays, the inset shows the response of 7-azaindole monomer in CDCl3.

6. Pump-probe signals of 7-azaindole dimer exhibit coherent wavepacket motions due to the in-plane stretching hydrogen bond mode of the dimer.

7. We use oligomers with 23 adenine-thymine base pairs with surfactant counterions to prepare optcally transparent DNA films with a water content controlled by varying the relative humidity in a specially designed sample holder. The IR spectra as function of relative humidity show pronounced humidity-dependent spectral features in the N-H/O-H stretching and in the symmetric and asymmetric phosphate stretching regions.

8. In the case of 0% relative humidity, with an average of 2 water molecules per base pair, the spectral substructure in the steady state spectrum (upper panel) can be dissected into bleach features due to the symmetric and asymmetric N-H stretching modes of adenine and the N-H sretching mode of thymine (central panel), and in a broad featureless component due to the O-H stretching mode of the residual water (lower panel). All these spectral features do not exhibit spectral diffusion up to several picoseconds, indicative of well-defined geometries on these time scales.

9. With polarization-sensitive pump-probe measurements the anisotropy decay curves can be determined. From these results it follows that the 3200 cm-1 bleach results from the symmetric N-H stretching of adenine and the N-H stretching of thymine exhibiting ultrafast excitation transfer. The 3350 cm-1 bleach component indicates the asymmetric N-H stretching transition of adenine, having smaller couplings with the other N-H stretching modes in the AT base pairs. The O-H stretching band of water around 3550 cm-1 does not show any anisotropy loss, in accordance with a location near the phosphate ionic heads, with no rotational diffusion occuring on time scales up to several picoseconds.

Ultrafast response of the oxygen K-edge of neat liquid water upon a temperature jump

10. Ultrafast IR-pump X-ray probe spectroscopy using an Ti:sapphire amplified laser system and parametric frequency conversion to generate femtosecond IR pump pulses and the Bessy storage ring to generate soft-X-ray pulses used for probing x-ray absorption near edge and extended absorption fine structure.

11. X-ray spectrum of th oxygen K edge of liquid water, showing pre-edge, main-edge and post-edge features indicative of the hydrogen bonding network structure. Transient X-ray transmission change at the pre-edge, upon IR-pumping of the O-H stretching intramolecular mode of liquid water, resulting in an ultrafast temperature jump with a decrease of the average hydrogen bonding coordination number of the water molecules.

Publications on coherent vibrational response in hydrogen bonds

DSN08b C1-P-2008.05   J. R. Dwyer, Lukasz Szyc, E. T. J. Nibbering and T. Elsaesser.   Ultrafast vibrational dynamics of adenine-thymine base pairs in hydrated DNA.   in Ultrafast Phenomena XVI, Springer Ser. Chem. Phys. 92, P. Corkum, S. De Silvestri, K. A. Nelson, E. Riedle and R. Schoenlein, eds., pp. 535-537 (Springer, Berlin, Germany, 2009).   Download PDF/PS-File or URL: C1-P-2008.05   GWG08 C1-P-2008.04   G. Gavrila, Ph. Wernet, K. Godehusen, C. Weniger, E. T. J. Nibbering, T. Elsaesser and W. Eberhardt.   Ultrafast temperature jumps in liquid water studied by a infrared-pump and x-ray absorption-probe spectroscopy.   in Ultrafast Phenomena XVI, Springer Ser. Chem. Phys. 92, P. Corkum, S. De Silvestri, K. A. Nelson, E. Riedle and R. Schoenlein, eds., pp. 505-507 (Springer, Berlin, Germany, 2009).   Download PDF/PS-File or URL: C1-P-2008.04   Els09b C0-P-2009.01   T. Elsaesser.   Two-dimensional infrared spectroscopy of intermolecular hydrogen bonds in the condensed phase.   Acc. Chem. Res. 42 (2009) 1220-1228   Download PDF/PS-File or URL: C1-P-2009.01   Els09a C0-P-2009.02   T. Elsaesser.   Ultrafast memory loss and relaxation processes in hydrogen bonded systems.   Biol. Chem. 390 (2009) 1125-1132   Download PDF/PS-File or URL: C1-P-2009.02   RIE09 C1-P-2009.05   R. Rey, F. Ingrosso, T.Elsaesser and J. T. Hynes   Pathways for H2O bend vibrational relaxation in liquid water.   J. Phys. Chem. A 113 (2009) 8949-8962   Download PDF/PS-File or URL: C0-P-2009.05   IRE09 C1-P-2009.04   F. Ingrosso, R. Rey, T. Elsaesser and J. T. Hynes   Ultrafast energy transfer from the intramolecular bending vibration to librations in liquid water.   J. Phys. Chem. A 113 (2009) 6657-6665   Download PDF/PS-File or URL: C0-P-2009.04   GGW09 C1-P-2008.14   G. Gavrila, K. Godehusen, C. Weniger, E. T. J. Nibbering, T. Elsaesser, W. Eberhardt and Ph. Wernet.   Time-resolved x-ray spectroscopy of infrared-laser induced temperature jumps in liquid water.   Appl. Phys. A 96 (2009) 11-18   Download PDF/PS-File or URL: C1-P-2008.14   SDN09 C1-P-2008.10   L. Szyc, J. R. Dwyer, E. T. J. Nibbering and T. Elsaesser.   Ultrafast dynamics of N-H and O-H stretching excitations in hydrated DNA oligomers.   Chem. Phys. 357 (2009) 36-44   Download PDF/PS-File or URL: C1-P-2008.10   DSN08a C1-P-2008.08   J. R. Dwyer, L. Szyc, E. T. J. Nibbering and T. Elsaesser.   Ultrafast vibrational dynamics of adenine-thymine base pairs in DNA oligomers.   J. Phys. Chem. B 112 (2008), 11194-11197   Download PDF/PS-File or URL: C1-P-2008.08   WGG08 C1-P-2008.01   Ph. Wernet, G. Gavrila, K. Godehusen, C. Weniger, E. T. J. Nibbering, T. Elsaesser and W. Eberhardt   Ultrafast temperature jump in liquid water studied by a novel infrared pump - x-ray probe technique.   Appl. Phys. A 92 (2008) 511-516   Download PDF/PS-File or URL: C1-P-2008.01   Els08 C0-P-2008.01   T. Elsaesser.   Ultrafast structural dynamics of hydrogen bonds in the liquid phase.   L'Actualité Chimique 320/321 (2008) 27-32   Download PDF/PS-File or URL: C0-P-2008.01   KCP08 C1-P-2007.08   D. Kraemer, M. L. Cowan, A. Paarmann, N. Huse, E. T. J. Nibbering, T. Elsaesser and R. J. Dwayne Miller.   Temperature dependence of the two-dimensional infrared spectrum of liquid H2O.   Proc. Natl. Acad. Sci. USA 105 (2008) 437-442   Download PDF/PS-File or URL: C1-P-2007.08   EHD07 C1-P-2007.05   T. Elsaesser, N. Huse, J. Dreyer, J. R. Dwyer, K. Heyne and E. T. J. Nibbering.   Ultrafast vibrational dynamics and anharmonic couplings of hydrogen-bonded dimers in solution.   Chem. Phys. 341 (2007) 175-188   Download PDF/PS-File or URL: C1-P-2007.05   PCK07 C1-P-2006.05   A. Paarmann, D. Kraemer, M. L. Cowan, N. Huse, M. Harb, B. D. Bruner, J. R. Dwyer, E. T. J. Nibbering, T. Elsaesser and R. J. D. Miller.   2D-IR photon echo spectroscopy of liquid H2O - Combination of novel nanofluidics and diffractive optics deciphers ultrafast structural dynamics.   in Ultrafast Phenomena XV, Springer Ser. Chem. Phys. 88, P. Corkum, D. Jonas, R. J. D. Miller and A. M. Weiner, eds., pp. 335-337 (Springer, Berlin, Germany, 2007).   Download PDF/PS-File or URL: C1-P-2006.05   AHN07 C1-P-2006.02   S. Ashihara, N. Huse, E. T. J. Nibbering and T. Elsaesser.   Ultrafast relaxation dynamics of O-H bending and librational excitations in liquid H2O.   in Ultrafast Phenomena XV, Springer Ser. Chem. Phys. 88, P. Corkum, D. Jonas, R. J. D. Miller and A. M. Weiner, eds., pp. 436-438 (Springer, Berlin, Germany, 2007).   Download PDF/PS-File or URL: C1-P-2006.02   NDK07 C1-P-2006.11   E. T. J. Nibbering, J. Dreyer, O. Kühn, J. Bredenbeck, P. Hamm and T. Elsaesser.   Vibrational dynamics of hydrogen bonds.   in: Analysis and Control of Ultrafast Photoinduced Reactions, O. Kühn, L. Wöste eds. Springer Series in Chemical Physics Vol. 87 (Springer Berlin 2007) pp. 619-687   Download PDF/PS-File or URL: C1-P-2006.11   AHE07 C1-P-2006.13   S. Ashihara, N. Huse, A. Espagne, E. T. J. Nibbering and T. Elsaesser.   Ultrafast structural dynamics of water induced by dissipation of vibrational energy.   J. Phys. Chem. A 111 (2007) 743-746   Download PDF/PS-File or URL: C1-P-2006.13   DDN06 C1-P-2006.12   J. R. Dwyer, J. Dreyer, E. T. J. Nibbering and T. Elsaesser.   Ultrafast dynamics of vibrational N-H stretching excitations in the 7-azaindole dimer   Chem. Phys. Lett. 432 (2006) 146-151   Download PDF/PS-File or URL: C1-P-2006.12   Els06a C0-P-2004.02   T. Elsaesser.   Coherent low-frequency motions in condensed phase hydrogen bonding and transfer   in Handbook of Hydrogen Transfer Reactions; Vol. 2: Physical and Chemical Aspects 2, J. T. Hynes, J. P. Klinman, H.-H. Limbach and R. L. Schowen, eds., pp. 459-477,(Wiley-VCH, Weinheim, Germany, 2006)   Download PDF/PS-File or URL:   AHE06 C1-P-2006.01   S. Ashihara, N. Huse, A. Espagne, E. T. J. Nibbering and T. Elsaesser.   Vibrational couplings and ultrafast relaxation of the O-H bending mode in liquid H2O.   Chem. Phys. Lett. 424 (2006) 66-70   Download PDF/PS-File or URL: C1-P-2006.01   EHH06 C1-P-2003.15   T. Elsaesser, K. Heyne, N. Huse and E. T. J. Nibbering.   Ultrafast vibrational dynamics of hydrogen bonded dimers in solution   in Time Resolved Vibrational Spectroscopy XI, S. Califano, P. Foggi and R. Righini, eds. , pp. 69-75 (Leo S. Olschki, Citta di Castello, Italy, 2006)   NBC05 C1-P-2004.17   N. Huse, B. D. Bruner, M. L. Cowan, J. Dreyer, E. T. J. Nibbering, R. J. D. Miller and T. Elsaesser.   Anharmonic coupling underlying ultrafast vibrational dynamics of hydrogen bonds in liquids.   Phys. Rev. Lett. 95 (2005) 147402/1-4.   Download PDF/PS-File or URL: C1-P-2004.17   HBC05 C1-P-2004.12   N. Huse, B. D. Bruner, M. L. Cowan, J. Dreyer, E. T. J. Nibbering, T. Elsaesser, and R. J. D. Miller.   Heterodyne 2D-IR photon echo spectroscopy of multi-level OH stretching coherences in hydrogen bonds.   in Ultrafast Phenomena XIV, Springer Ser. Chem. Phys. 79, T. Kobayashi, T. Okada, T. Kobayashi, K. A. Nelson and S. De Silvestri, eds., pp. 407-409 (Springer, Berlin, 2005).   Download PDF/PS-File or URL: C1-P-2004.12   HPN05 C1-P-2004.11   K. Heyne, M. Petkovi, E. T. J. Nibbering, O. Kühn and T. Elsaesser.   Cascaded energy redistribution upon O-H stretch excitation in an intramolecular hydrogen bonded system.   in Ultrafast Phenomena XIV, Springer Ser. Chem. Phys. 79, T. Kobayashi, T. Okada, T. Kobayashi, K. A. Nelson and S. De Silvestri, eds., pp. 389-391 (Springer, Berlin, 2005).   Download PDF/PS-File or URL: C1-P-2004.11   HAN05 C1-P-2005.03   N. Huse, S. Ashihara, E. T. J. Nibbering and T. Elsaesser   Ultrafast vibrational relaxation of O-H bending and librational excitations in liquid H2O.   Chem. Phys. Lett. 404 (4-6), 389-393 (2005).   Download PDF/PS-File or URL: C1-P-2005.03   CBH05 C1-P-2004.16   M. L. Cowan, B. D. Bruner, N. Huse, J. R. Dwyer, B. Chugh, E. T. J. Nibbering, T. Elsaesser and R. J. D. Miller.   Ultrafast memory loss and energy redistribution in the hydrogen bond network of liquid H2O.   Nature 434 (7030), 199-202 (2005).   Download PDF/PS-File or URL: C1-P-2004.16   HNE04 C1-P-2004.03   K. Heyne, E. T. J. Nibbering, T. Elsaesser, M. Petkovi and O. Kühn.   Cascaded energy redistribution upon O-H stretching excitation in an intramolecular hydrogen bond.   J. Phys. Chem. A 108 (29), 6083-6086 (2004).   Download PDF/PS-File or URL: C1-P-2004.03   HHD04 C1-P-2004.02   K. Heyne, N. Huse, J. Dreyer, E. T. J. Nibbering, T. Elsaesser and S. Mukamel.   Coherent low-frequency motions of hydrogen bonded acetic acid dimers in the liquid phase.   J. Chem. Phys. 121 (2), 902-913 (2004).   Download PDF/PS-File or URL: C1-P-2004.02   ELSa04 C1-P-2003.14   T. Elsaesser, K. Heyne, N. Huse and E. T. J. Nibbering.   Ultrafast vibrational dynamics of hydrogen-bonded dimers in solution.   in Femtochemistry and Femtobiology: Ultrafast Events in Molecular Science, M. Martin, J. T. Hynes, eds., pp. 157-164 (Elsevier, Amsterdam, the Netherlands, 2004).   NE04 C1-P-2003.04   E. T. J. Nibbering and T. Elsaesser.    Ultrafast vibrational dynamics of hydrogen bonds in the condensed phase.   Chem. Rev. 104 (4), 1887-1914 (2004).   Download PDF/PS-File or URL: C1-P-2003.04   HHN03c C1-P-2003.08    K. Heyne, N. Huse, E. T. J. Nibbering and T. Elsaesser    Ultrafast relaxation and anharmonic coupling of O-H stretching and bending excitations in cyclic acetic acid dimers   Chem. Phys. Lett. 382 (2003) 19-25   Download PDF/PS-File or URL: C1-P-2003.08   HHD03 C1-P-2002.17   N. Huse, K. Heyne, J. Dreyer, E. T. J. Nibbering and T. Elsaesser    Vibrational multi-level quantum coherence due to anharmonic couplings in intermolecular hydrogen bonds   Phys. Rev. Lett. 91 (2003) 197401/1-4   Download PDF/PS-File or URL: C1-P-2002.17   HHN03a C1-P-2002.12   K. Heyne, N. Huse, E. T. J. Nibbering and T. Elsaesser    Ultrafast coherent nuclear motions of hydrogen bonded carboxylic acid dimers   Chem. Phys. Lett. 369 (2003) 591-596   Download PDF/PS-File or URL: C1-P-2002.12   HHN03b C1-P-2002.16   K. Heyne, N. Huse, E. T. J. Nibbering and T. Elsaesser    Coherent vibrational dynamics of intermolecular hydrogen bonds in acetic acid dimers studied by ultrafast mid-infrared spectroscopy   J. Phys.: Condens. Matter 15 (2003) 129-136   Download PDF/PS-File or URL: C1-P-2002.16   SMH03 C1-P-2002.07   J. Stenger, D. Madsen, P. Hamm, E. T. J. Nibbering and T. Elsaesser     A mid-infrared photon echo study of liquid water     in Ultrafast Phenomena XIII, Springer Ser. Chem. Phys. 71, R. D. Miller, M. M. Murnane, N. F. Scherer and A. M. Weiner, Eds. (Springer Verlag, Berlin, 2003) pp. 577-579   SMD02b C1-P-2001.18   J. Stenger, D. Madsen, J. Dreyer, E. T. J. Nibbering, P. Hamm and T. Elsaesser   Ultrafast dynamics of hydrogen bonds in the liquid phase: Vibrational quantum beats and dephasing   in Femtochemistry and Femtobiology, A. Douhal and J. Santamaria, eds. (World Scientific, Singapore, 2002), pp. 169-184   MSD02 C1-P-2001.16    D. Madsen, J. Stenger, J. Dreyer, P. Hamm, E. T. J. Nibbering and T. Elsaesser    Femtosecond mid-infrared pump-probe study of wave packet motion in a medium-strong intramolecular hydrogen bond   Bull. Chem. Soc. Jpn. 75 (2002) 909-917   Download PDF/PS-File or URL: C1-P-2001.16   SMD02a C1-P-2001.19    J. Stenger, D. Madsen, J. Dreyer, P. Hamm, E. T. J. Nibbering and T. Elsaesser    Femtosecond mid-infrared photon echo study of an intramolecular hydrogen bond   Chem. Phys. Lett. 354 (2002) 256-263   Download PDF/PS-File or URL: C1-P-2001.19   SMH02  C1-P-2001.11   J. Stenger, D. Madsen, P. Hamm, E. T. J. Nibbering and T. Elsaesser    A photon echo peak shift study of liquid water   J. Phys. Chem. A 106 (2002) 2341-2350   Download PDF/PS-File or URL: C1-P-2001.11   SMH01 C1-P-2001.03   J. Stenger, D. Madsen, P. Hamm, E. T. J. Nibbering and T. Elsaesser    Ultrafast vibrational dephasing of liquid water   Phys. Rev. Lett. 87 (2001) 027401   Download PDF/PS-File or URL: C1-P-2001.03   MSD01 C1-P-2001.06   D. Madsen, J. Stenger, J. Dreyer, E. T. J. Nibbering, P. Hamm and T. Elsaesser    Coherent vibrational ground-state dynamics of an intramolecular hydrogen bond   Chem. Phys. Lett. 341 (2001) 56-62   Download PDF/PS-File or URL: C1-P-2001.06   SMD01 C1-P-2000.09    J. Stenger, D. Madsen, J. Dreyer, E. T. J. Nibbering, P. Hamm and T. Elsaesser    Coherent response of hydrogen bonds in liquids probed by ultrafast vibrational spectroscopy   J. Phys. Chem. A 105 (2001) 2929-2932   Download PDF/PS-File or URL: C1-P-2000.09   SMD00 C1-P-2000.19    J. Stenger, D. Madsen, J. Dreyer, E. T. J. Nibbering, P. Hamm and T. Elsaesser   Ultrafast coherent response of hydrogen bonds   in Ultrafast Phenomena XII, Springer Ser. Chem. Phys. 66, T. Elsaesser, S. Mukamel, M. M. Murnane, N. F. Scherer, Eds. (Springer Verlag, Berlin, 2000), pp. 542-544