Erik T J Nibbering

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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(More)
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 approximately 1 ps. Room temperature measurements show a loss of frequency and, thus, structural(More)
We investigate with femtosecond mid-infrared spectroscopy the vibrational-mode characteristics of the electronic states involved in the excited-state dynamics of pyranine (HPTS) that ultimately lead to efficient proton (deuteron) transfer in H2O (D2O). We also study the methoxy derivative of pyranine (MPTS), which is similar in electronic structure but does(More)
The proton transfer mechanism between aqueous Brønsted acids and bases, forming an encounter pair, has been studied in real time with ultrafast infrared spectroscopy. The transient intermediacy of a hydrated proton, formed by ultrafast dissociation from an optically triggered photoacid proton donor ROH, is implicated by the appearance of an infrared(More)
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(More)
The neutralization reaction between an acid and a base in water, triggered after optical excitation, was studied by femtosecond vibrational spectroscopy. Bimodal dynamics were observed. In hydrogen-bonded acid-base complexes, the proton transfer proceeds extremely fast (within 150 femtoseconds). In encounter pairs formed by diffusion of uncomplexed(More)
We used femtosecond infrared polarization spectroscopy and density functional theory in a study on the key signaling molecule nitric oxide (NO) bound to myoglobin. Our results show that after photolysis, a substantial fraction of NO recombines within the first few picoseconds. We discovered that the diatomic ligand is severely tilted in the protein and(More)
We characterize the structural and electronic changes during the photoinduced enol-keto tautomerization of 2-(2'-hydroxyphenyl)-benzothiazole (HBT) in a nonpolar solvent (tetrachloroethene). We quantify the redistribution of electronic charge and intramolecular proton translocation in real time by combining UV-pump/IR-probe spectroscopy and quantum chemical(More)
Time-resolved infrared (IR) and Raman spectroscopy elucidates molecular structure evolution during ultrafast chemical reactions. Following vibrational marker modes in real time provides direct insight into the structural dynamics, as is evidenced in studies on intramolecular hydrogen transfer, bimolecular proton transfer, electron transfer, hydrogen bonding(More)