title: Picosecond calorimetry: time-resolved x-ray diffraction studies of liquid CH2Cl2.
abstract: Liquid phase time-resolved x-ray diffraction with 100 ps resolution has recently emerged as a powerful technique for probing the structural dynamics of transient photochemical species in solution. It is intrinsic to the method, however, that a structural signal is observed not only from the photochemical of interest but also from the embedding solvent matrix. To experimentally characterize the x-ray diffraction signal deriving from the solvent alone we performed time-resolved diffraction studies of a pure liquid sample over a time domain from -250 ps to 2.5 micros. Multiphoton excitation was used to rapidly heat liquid CH(2)Cl(2) using UV pulses of 100 fs duration. A significant x-ray diffraction signal is visible prior to the onset of thermal expansion, which characterizes a highly compressed superheated liquid. Liquid CH(2)Cl(2) then expands as a shock wave propagates through the sample and the temporal dependence of this phenomenon is in good agreement with theory. An unexpectedly slow initial release of energy into the liquid as heat is observed from multiphoton excited CH(2)Cl(2), revealing the presence of a metastable state of multiphoton excited CH(2)Cl(2).
authors.affiliation: Department of Photochemistry and Molecular Science, Uppsala University, Box 523, S-7123 Uppsala, Sweden.
authors.forename: Panayiotis
authors.initials: P
authors.lastname: Georgiou
authors.forename: Jonathan
authors.initials: J
authors.lastname: Vincent
authors.forename: Magnus
authors.initials: M
authors.lastname: Andersson
authors.forename: Annemarie B
authors.initials: AB
authors.lastname: Wöhri
authors.forename: Pontus
authors.initials: P
authors.lastname: Gourdon
authors.forename: Jens
authors.initials: J
authors.lastname: Poulsen
authors.forename: Jan
authors.initials: J
authors.lastname: Davidsson
authors.forename: Richard
authors.initials: R
authors.lastname: Neutze