/de/research/projects/3.1/topics/Topic2/index-topic2.html
3.1 Dynamics of Condensed Phase Molecular Systems
Project coordinator(s): E. Nibbering, O. Kornilov
Topic 2: Transient structure determination of hydrogen bonded acid-base pairs

 

The people involved: Maria Ekimova, Erik T. J. Nibbering
Former team members: Mirabelle Prémont-Schwarz, Christian Greve, Rene Costard, Henk Fidder, Benjamin Koeppe, Peter M. Tolstoy

National and international collaboration: Brian T. Psciuk,#Dequan Xiao,# Victor S. Batista,# Sharon Keinan, Dina Pines, Ehud Pines , Peter M. Tolstoy M. Odelius,* Simon Schreck,+ Wilson Quevedo,+ Markus Kubin,+Philippe Wernet+
: Department of Chemistry, Ben Gurion University of the Negev, Beer-Sheva, 84105 Israel
#: Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, United States of America
º: Department of Chemistry, St. Petersburg University, Russian Federation
*: Department of Physics, Stockholm Universitet, Stockholm, Sweden
+: Ultrafast X-Ray Science Group, Helmholtz-Zentrum Berlin, BESSY II, Albert-Einstein-Str. 15, D-12489 Berlin, Germany

Photoacids are molecular systems that exhibit a pronounced increase in acidity upon electronic excitation, enabling proton transfer dynamics to be studied in real time using time-resolved spectroscopy (see also Topic 3). The goal of the project is to combine the structure resolving potential of time-resolved IR and x-ray spectroscopies to determine hydrogen bond geometries of photoacid-base complexes in liquid solution, and the changes of these hydrogen bond geometries upon electronic excitation of the photoacid chromophores. To support this research hydrogen bond dynamics of acid-base complexes in the electronic ground state will be performed as well, building on our achievements on ultrafast IR spectroscopy of hydrogen-bonded molecular systems (see also Topic 1, in particular earlier phases, here and here). Third party funding comes since 2012 from the Deutsche Forschungsgemeinsschaft (DFG Normalverfahren NI 492/11-1) and since 2016 from the Leibniz Gemeinschaft (SAW-2016-1).



1. Photoacid Förster Cycle, linking optical spectroscopy to changes in acidity upon electronic excitation
 


2. Experimental methods used to characterize transient hydrogen bond dynamics in photoacid-base pairs.
 


3. 2D UV/NMR 2D correlation analysis of an acid-base complex, measured at 180 K in CD2Cl2.
 


4. Electronic transitions in naphthalene (N), 1-naphthol (1N) and 2-naphthol (2N) are compared with quantum chemical calculations using (TD-)DFT.
 


5. Steady-state and transient IR spectra of 1-naphthol and 2-naphthol. The solvent induced frequency shift is plotted as a function of the dielectric function F0, upper panel experimental results fitted, middle panel experimental results compared with the perturbative theory by Pullin (1958) with molecular parameters calculated using (TD-)DFT, lower panel experimental results compared with (TD-)DFT calculations using continuum solvent models as implemented in Gaussian09.
 


6. Experimental and theoretical O-H stretching frequency shift as determined for 2-naphthol in the electronic ground and first excited states, plus a series of substituted phenols and naphthols, hydrogen bonded to acetonitrile. The coupling of the molecular complexes with the solvent was modelled in the same fashion as for the uncomplexed naphthols.
 


7. Correlating photoacidity to hydrogen bond structure: The gas-phase value of the O-H stretching mode (intercept at F0 = 0 in Figure 6) correlates with acidity (as characterized by the pKa-value) as well as O..N and O-H bond distances.
 



8. Species-dependent linear FT-IR spectra of aniline-d5 (An) as monomer (black lines), single hydrogen-bonded complex with DMSO (red lines) and double hydrogen-bonded complex (blue lines).The hydrogen bond enhancement of the Fermi resonance between the N-H stretching modes and the d(NH2) bending overtone or the n(C=C) stretching + d(NH2) bending combination tone is clearly pronounced.

 


9. 2D-IR Spectra of aniline-d5 (An) as monomer (black lines), single hydrogen-bonded complex with DMSO (red lines) and double hydrogen-bonded complex (blue lines) for two different polarization conditions of the applied laser pulses in the three-pulse photon echo measurement at population waiting time T = 125 fs...
 


10. Combined study of steady-state IR spectra of the N-H stretching mode and of the N K-edge spectra of N-methylaniline in acetone and in DMSO.
 


11. Liquid flatjet for use in solution phase soft-x-ray spectroscopy.
 


12. Comparison of measured O K-edge spectra with the atomic cross section data shows a liquid flatjet with 1-2 µm thickness. This flatjet is an exquisite tool for solution phase soft-x-ray spectroscopy, as shown with measurements on the N K-edge of aqueous ammonium.
 

Publications on

Transient structure determination of hydrogen bonded acid-base pairs

 
EQF15
C1-P-2015.04
  M. Ekimova, W. Quevedo, M. Faubel, Ph. Wernet and E. T. J. Nibbering..
 
A liquid flatjet system for solution phase soft-X-ray spectroscopy.
 
Structural Dynamics 2 (2015) 054301/1-13
 
Download PDF/PS-File or URL: C1-P-2015.04
 
PSI15
C1-P-2015.02
  M. Prémont-Schwarz, S. Schreck, M. Iannuzzi, E. T. J. Nibbering, M. Odelius and Ph. Wernet.
 
Correlating infrared and x-ray absorption energies for molecular-level insight into hydrogen bond making and breaking in solution.
 
J. Phys. Chem. B 119 (2015) 8115-8124
 
Download PDF/PS-File or URL: C1-P-2015.02
 
PPK15b
C1-P-2015.01
  B. Psciuk, M. Prémont-Schwarz, B. Koeppe, S. Keinan, D. Xiao, E. T. J. Nibbering and V. S. Batista.
 
Correlating photoacidity to hydrogen-bond structure by using the local O-H stretching probe in hydrogen-bonded complexes of aromatic alcohols.
 
J. Phys. Chem. A 119 (2015) 4800- 4812
 
Download PDF/PS-File or URL: C1-P-2015.01
 
PPK15
C1-P-2014.04
  B. Psciuk, M. Prémont-Schwartz, B. Koeppe, S. Keinan, D. Xiao, V. S. Batista and E. T. J. Nibbering.
 
Ultrafast IR spectroscopy of O-H stretching modes in 2-naphthol-acetonitrile photoacid-base complexes.
 
n: Ultrafast Phenomena XIX, K. Yamanouchi, S. Cundiff, R. de Vivie-Riedle, M. Kuwata-Gonokami, L. DiMauro (Eds.), Springer, Heidelberg (2015) p. 483-486
 
Download PDF/PS-File or URL: C1-P-2014.04
 
GCF15
C1-P-2014.10
  C. Greve, R. Costard, H. Fidder and E. T. J. Nibbering.
 
Hydrogen bond enhancement of Fermi resonances explored with ultrafast IR two-colour pump-probe and 2D-IR spectroscopy.
 
in: Ultrafast Phenomena XIX, K. Yamanouchi, S. Cundiff, R. de Vivie-Riedle, M. Kuwata-Gonokami, L. DiMauro (Eds.), Springer, Heidelberg (2015) p. 471-474
 
Download PDF/PS-File or URL: C1-P-2014.10
 
CGF15
C1-P-2014.05
  R. Costard, C. Greve, H. Fidder and E. T. J. Nibbering.
 
Hydrogen bonding induced enhancement of Fermi resonances: ultrafast vibrational energy flow dynamics in aniline-d5.
 
J. Phys. Chem. B 119 (2015) 2711−2725
 
Download PDF/PS-File or URL: C1-P-2014.05
 
GNF13
C1-P-2013.07
  C. Greve, E.T.J. Nibbering and H. Fidder.
 
Hydrogen-bonding-induced enhancement of Fermi Resonances: A linear IR and nonlinear 2D-IR study of aniline-d5.
 
J. Phys. Chem. B 117 (2013) 15843-15855
 
Download PDF/PS-File or URL: C1-P-2013.07
 
MPB13
C1-P-2013.04
  F. Messina, M. Prémont-Schwarz, O. Braem, D. Xiao, V. S. Batista, E. T. J. Nibbering and M. Chergui.
 
Ultrafast solvent-assisted electronic level crossing in 1-naphthol.
 
Angew. Chem. 125 (2013) 7009–7013 and Angew. Chem. Int. Ed. 52 (2013) 6871–6875
 
Download PDF/PS-File or URL: C1-P-2013.04 and C1-P-2013.04
 
PXS13
C1-P-2012.05
  M. Prémont-Schwarz, D. Xiao, S. Sekharan, V. S. Batista and E. T. J. Nibbering.
 
Ultrafast OH stretching frequency shifts of hydrogen-bonded 2-naphthol photoacid-base complexes in solution.
 
in: Ultrafast Phenomena XVIII, M. Chergui, A. Taylor, S. Cundiff, R. de Vivie-Riedle, K. Yamagouchi (Eds.), EDP Sciences, (2013) p. 06007/1-3
 
Download PDF/PS-File or URL: C1-P-2012.05
 
XPN12
C1-P-2011.06
  D. Xiao, M. Prémont-Schwarz, E. T. J. Nibbering and V. S. Batista.
 
Ultrafast vibrational frequency shifts Induced by electronic excitations: Naphthols in low dielectric media.
 
J. Phys. Chem. A 116 (2012) 2775-2790
 
Download PDF/PS-File or URL: C1-P-2011.06
 
PXB11
C1-P-2011.05
  M. Prémont-Schwarz, D. Xiao, V. S. Batista and E. T. J. Nibbering.
 
The O–H stretching mode of a prototypical photoacid as a local dielectric probe.
 
J. Phys. Chem. A 115 (2011) 10511-10516
 
Download PDF/PS-File or URL: C1-P-2011.05
 
KTG11
C1-P-2011.01
  B. Koeppe, P. M. Tolstoy, J. Guo, E. T. J. Nibbering and T. Elsaesser.
 
Two-dimensional UV-vis/NMR correlation spectroscopy: A heterospectral signal assignment of hydrogen-bonded complexes.
 
J. Phys. Chem. Lett. 2 (2011) 1106-1110
 
Download PDF/PS-File or URL: C1-P-2011.01
 
 
 

Publications on intermolecular hydrogen-bonding dynamics (1998-2000)

 
NDr01 
C1-P-2000.13 
  E. T. J. Nibbering and J. Dreyer.

  Femtosecond chemical events of intramolecular charge transfer and intermolecular hydrogen bond breaking after electronic excitation: structural dynamics in the condensed phase

  in Femtochemistry, F. C. de Schryver, S. de Feyter, and G. Schweitzer, Eds., (Wiley-VCH, Weinheim, Germany, 2001) pp. 345-366
 
NEl00
C1-P-2000.14 
  E. T. J. Nibbering and T. Elsaesser. 

  Probing solvation dynamics with femtosecond vibrational spectroscopy

  Appl. Phys. B 71 (2000) 439-41

  Download PDF/PS-File or URL: C1-P-2000.14
 
NTC00
C1-P-1999.15 
  E. T. J. Nibbering, F. Tschirschwitz, C. Chudoba and T. Elsaesser. 

  Femtochemistry of hydrogen-bonded complexes after electronic excitation in the liquid phase: the case of coumarin 102

  J. Phys. Chem. A 104 (2000) 4236-4246

  Download PDF/PS-File or URL: C1-P-1999.15
 
TNi99 
C1-P-1999.04

  F. Tschirschwitz and E. T. J. Nibbering. 

  Femtosecond pump-probe and grating scattering study of condensed phase hydrogen-bonding dynamics of complexes of coumarin 102

  Chem. Phys. Lett. 312 (1999) 169-177

  Download PDF/PS-File or URL: C1-P-1999.04
 
CNE99
C3-P-1999.02
 
  C. Chudoba, E. T. J. Nibbering and T. Elsaesser. 

  Ultrafast structural response of hydrogen bonded complexes to electronic excitation in the liquid phase

  J. Phys. Chem. A 103 (1999) 5625-5628

  Download PDF/PS-File or URL: C3-P-1999.02
 
NCE99
C1-P-1999.01
 
  E. T. J. Nibbering, C. Chudoba and T. Elsaesser. 

  Hydrogen-bond dynamics and solvation of electronically excited-states determined by femtosecond vibrational spectroscopy

  Israel J. of Chem. 39 (1999) 333
 
CNE98b
C3-P-1998.09

  C. Chudoba, E. T. J. Nibbering and T. Elsaesser.
    Dynamics of site-specific excited-state solute-solvent interactions as probed by femtosecond vibrational spectroscopy
    in Ultrafast Phenomena XI, Springer Ser. Chem. Phys. 63, T. Elsaesser, D. Wiersma, J. Fujimoto and W. Zinth, Eds. (Springer Verlag Berlin (1998) 535-537
 
CNE98a
C3-P-1998.07
 
  C. Chudoba, E. T. J. Nibbering and T. Elsaesser. 

  Site-specific excited-state solute-solvent interactions probed by femtosecond vibrational spectroscopy

  Phys. Rev. Lett. 81 (1998) 3010-3013

  Download PDF/PS-File or URL: C3-P-1998.07