Erik T. J. Nibbering
École Polytechnique
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Featured researches published by Erik T. J. Nibbering.
Nature | 2005
Michael L. Cowan; B. D. Bruner; Nils Huse; Jason R. Dwyer; B. Chugh; Erik T. J. Nibbering; Thomas Elsaesser; R. J. D. Miller
Many of the unusual properties of liquid water are attributed to its unique structure, comprised of a random and fluctuating three-dimensional network of hydrogen bonds that link the highly polar water molecules. One of the most direct probes of the dynamics of this network is the infrared spectrum of the OH stretching vibration, which reflects the distribution of hydrogen-bonded structures and the intermolecular forces controlling the structural dynamics of the liquid. Indeed, water dynamics has been studied in detail, most recently using multi-dimensional nonlinear infrared spectroscopy for acquiring structural and dynamical information on femtosecond timescales. But owing to technical difficulties, only OH stretching vibrations in D2O or OD vibrations in H2O could be monitored. Here we show that using a specially designed, ultrathin sample cell allows us to observe OH stretching vibrations in H2O. Under these fully resonant conditions, we observe hydrogen bond network dynamics more than one order of magnitude faster than seen in earlier studies that include an extremely fast sweep in the OH frequencies on a 50-fs timescale and an equally fast disappearance of the initial inhomogeneous distribution of sites. Our results highlight the efficiency of energy redistribution within the hydrogen-bonded network, and that liquid water essentially loses the memory of persistent correlations in its structure within 50 fs.
Optics Letters | 1996
Erik T. J. Nibbering; P. F. Curley; G. Grillon; Bernard Prade; Michel Franco; F. Salin; A. Mysyrowicz
Conical emission in the forward direction is observed from intense femtosecond light pulses propagating through air over long distances. The conical emission is attributed to Cerenkov radiation from a dynamic self-guiding structure consisting of a weakly ionized core surrounded by Kerr cladding.
Proceedings of the National Academy of Sciences of the United States of America | 2008
Darren Kraemer; Michael L. Cowan; Alexander Paarmann; Nils Huse; Erik T. J. Nibbering; Thomas Elsaesser; R. J. Dwayne Miller
Two-dimensional infrared photon-echo measurements of the OH stretching vibration in liquid H2O are performed at various temperatures. Spectral diffusion and resonant energy transfer occur on a time scale much shorter than the average hydrogen bond lifetime of ≈1 ps. Room temperature measurements show a loss of frequency and, thus, structural correlations on a 50-fs time scale. Weakly hydrogen-bonded OH stretching oscillators absorbing at high frequencies undergo slower spectral diffusion than strongly bonded oscillators. In the temperature range from 340 to 274 K, the loss in memory slows down with decreasing temperature. At 274 K, frequency correlations in the OH stretch vibration persist beyond ≈200 fs, pointing to a reduction in dephasing by librational excitations. Polarization-resolved pump-probe studies give a resonant intermolecular energy transfer time of 80 fs, which is unaffected by temperature. At low temperature, structural correlations persist longer than the energy transfer time, suggesting a delocalization of OH stretching excitations over several water molecules.
Science | 2009
Katrin Adamczyk; Mirabelle Prémont-Schwarz; Dina Pines; Ehud Pines; Erik T. J. Nibbering
A Glimpse of Wet Carbonic Acid Both carbon dioxide and bicarbonate play extraordinarily widespread roles in biochemical and geochemical reactions. It is surprising therefore that carbonic acid, the intermediate in the water-coupled interconversion of these two compounds, has never been directly characterized in aqueous solution. Adamczyk et al. (p. 1690, published online 12 November) have succeeded in glimpsing the elusive acid by inducing an aqueous photoacid (a compound rendered transiently more acidic upon light absorption) to react with dissolved bicarbonate. Using infrared spectroscopy, they show that the carbonic acid product persists for nanoseconds. Analysis of its formation kinetics affords a direct pKa value of 3.5, substantially lower than the effective value derived from observations of the net bicarbonate/carbon dioxide equilibrium. The use of a photoacid enables the long-sought characterization of the conjugate acid of bicarbonate. Despite the widespread importance of aqueous bicarbonate chemistry, its conjugate acid, carbonic acid, has remained uncharacterized in solution. Here we report the generation of deuterated carbonic acid in deuterium oxide solution by ultrafast protonation of bicarbonate and its persistence for nanoseconds. We follow the reaction dynamics upon photoexcitation of a photoacid by monitoring infrared-active marker modes with femtosecond time resolution. By fitting a kinetic model to the experimental data, we directly obtain the on-contact proton-transfer rate to bicarbonate, previously inaccessible with the use of indirect methods. A Marcus free-energy correlation supports an associated pKa (Ka is the acid dissociation constant) of 3.45 ± 0.15, which is substantially lower than the value of 6.35 that is commonly assumed on the basis of the overall carbon dioxide–to–bicarbonate equilibrium. This result should spur further exploration of acid-base reactivity in carbon dioxide–rich aqueous environments such as those anticipated under sequestration schemes.
Journal of Chemical Physics | 2004
Karsten Heyne; Nils Huse; Jens Dreyer; Erik T. J. Nibbering; Thomas Elsaesser; Shaul Mukamel
Ultrafast vibrational dynamics of cyclic hydrogen bonded dimers and the underlying microscopic interactions are studied in temporally and spectrally resolved pump-probe experiments with 100 fs time resolution. Femtosecond excitation of the O-H and/or O-D stretching mode gives rise to pronounced changes of the O-H/O-D stretching absorption displaying both rate-like kinetic and oscillatory components. A lifetime of 200 fs is measured for the v=1 state of the O-H stretching oscillator. The strong oscillatory absorption changes are due to impulsively driven coherent wave packet motions along several low-frequency modes of the dimer between 50 and 170 cm(-1). Such wave packets generated via coherent excitation of the high-frequency O-H/O-D stretching oscillators represent a clear manifestation of the anharmonic coupling of low- and high-frequency modes. The underdamped low-frequency motions dephase on a time scale of 1-2 ps. Calculations of the vibrational potential energy surface based on density functional theory give the frequencies, anharmonic couplings, and microscopic elongations of the low-frequency modes, among them intermolecular hydrogen bond vibrations. Oscillations due to the excitonic coupling between the two O-H or O-D stretching oscillators are absent as is independently confirmed by experiments on mixed dimers with uncoupled O-H and O-D stretching oscillators.
Optics Letters | 1998
H. R. Lange; G. Grillon; J.-F. Ripoche; Michel Franco; Brigitte Lamouroux; Bernard Prade; A. Mysyrowicz; Erik T. J. Nibbering; Arnaud Chiron
Self-guided propagation of femtosecond laser pulses is studied for a converging-beam configuration. Channeling of the pulse energy through various gases is observed over distances well beyond the lens focal point, a fact that cannot be explained by the moving-focus model. The results are in good agreement with three-dimensional numerical simulations.
Optics Communications | 1997
J.-F. Ripoche; G. Grillon; Bernard Prade; Michel Franco; Erik T. J. Nibbering; Rüdiger Lange; A. Mysyrowicz
Abstract Using cross-phase modulation, the dynamics of the Kerr-like response of air is studied. Spontaneous resurgences of the induced non-linear polarisation are observed, in good agreement with a theoretical model.
Optics Communications | 1995
Erik T. J. Nibbering; Michel Franco; Bernard Prade; G. Grillon; C. Le Blanc; A. Mysyrowicz
A fast and accurate method for the measurement of the nonlinear refractive index of transparent materials is presented. The method is applied to various solids and liquids. The effective femtosecond response time of the optical Kerr effect in benzene and methanol is determined.
Chemical Physics Letters | 2003
Matteo Rini; Jens Dreyer; Erik T. J. Nibbering; Thomas Elsaesser
Abstract Vibrational spectra between 1000 and 1700 cm−1 are studied after ultrafast transfer of a hydrogen atom in the excited state of 2-(2′-hydroxyphenyl)benzothiazole. Femtosecond pump–probe experiments reveal new vibrational bands of the keto-S1 state, including the carbonyl stretching band formed by hydrogen transfer. Such bands display a negligible spectral reshaping but blue-shift by up to 7 cm−1 following biexponential kinetics with time constants of 700 fs and 15 ps. The blue-shift is attributed to the anharmonic coupling of the fingerprint vibrations to Raman-active low-frequency modes that are excited upon electronic excitation and depopulated by intramolecular redistribution and cooling to the solvent.
Chemical Physics Letters | 1999
Christian Chudoba; A. Kummrow; Jens Dreyer; Jens Stenger; Erik T. J. Nibbering; Thomas Elsaesser; Klaas A. Zachariasse
Abstract Combining femtosecond transient vibrational spectroscopy and high-level calculations is a powerful tool in the determination of excited-state structures. Striking differences in the experimental vibrational pattern of the locally excited states of 4-(dimethylamino)benzonitrile (DMABN) and 4-aminobenzonitrile (ABN) are explained on the basis of molecular structures obtained from ab initio complete-active-space self-consistent-field (CASSCF) calculations, giving evidence for a strong sensitivity of the molecular structure on modest changes in the substituents. The 4.0 ps charge-transfer time for DMABN in acetonitrile is resolved for the first time by tracking the downshifted CN stretching mode.