Photon Antibunching in a Cyclic Chemical Reaction Scheme.
The direct observation of chemical reactions on the single-molecule level is an ultimate goal in single-molecule chemistry, which also includes kinetic analyses. To analyze the lifetime of reaction intermediates, very sophisticated excitation schemes are often required. Here we focus on the kinetic analysis of the ground-state proton transfer within the photocycle of a photoacid. In detail, we demonstrate the determination of the bimolecular rate constant of this process with nanosecond resolution. The procedure relies on the exploration of a purely quantum-optical effect, namely, photon antibunching, and thus on evaluating interphoton arrival times to extract the reaction rate constant.
†Biophysikalische Chemie, Universität des Saarlandes, Campus B2.2, 66123 Saarbrücken, Germany.
Michael
M
Vester
†Biophysikalische Chemie, Universität des Saarlandes, Campus B2.2, 66123 Saarbrücken, Germany.
Tobias
T
Staut
‡III. Physikalisches Institut für Biophysik und Komplexe Systeme, Georg-August-Universität, Friedrich-Hund-Platz 1, 37077 Göttingen, Germany.
Jörg
J
Enderlein
†Biophysikalische Chemie, Universität des Saarlandes, Campus B2.2, 66123 Saarbrücken, Germany.
Gregor
G
Jung
D007700:Kinetics; D010777:Photochemistry; D017785:Photons
Förster cycle; chemical kinetics; excited-state proton transfer; fluorescence correlation spectroscopy; photochemistry; second-order correlation; single-molecule detection