Two-color reduced-Doppler (TCRD) and one-color velocity map imaging (VMI) were used for probing H atom photofragments resulting from the ~243.1 nm photodissociation of pyrrole. The velocity components of the H photofragments were probed by employing two counterpropagating beams at close and fixed wavelengths of 243.15 and 243.12 nm in TCRD and a single beam at ~243.1 nm, scanned across the Doppler profile in VMI. The TCRD imaging enabled probing of the entire velocity distribution in a single pulse, resulting in enhanced ionization efficiency, as well as improved sensitivity and signal-to-noise ratio. These advantages were utilized for studying the pyrrole photodissociation at ~243.1 and 225 nm, where the latter wavelength provided only a slight increase in the H yield over the self-signal from the probe beams. The TCRD imaging enabled obtaining high quality H(+) images, even for the low H photofragment yields formed in the 225 nm photolysis process, and allowed determining the velocity distributions and anisotropy parameters and getting insight into pyrrole photodissociation.
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http://dx.doi.org/10.1063/1.4828891 | DOI Listing |
J Phys Chem A
May 2016
Department of Physics, Ben-Gurion University of the Negev, Beer-Sheva 84105, Israel.
The room-temperature photoacoustic Raman and jet-cooled H action spectra, measured in the region of the fundamental CD3 stretches and the almost isoenergetic overtones or combinations of CD3 deformations in the methylamine-d3 (CD3NH2) isotopologue, show different relative intensities of the vibrational bands. The observed difference and the vibrational assignment point to favored ultraviolet excitation due to larger Franck-Condon (FC) factors from the deformation modes, leading to more effective N-H bond cleavage in CD3NH2 predissociation. The comparable measured two-color reduced-Doppler ion images and total kinetic energy distributions resulting from the predissociation of molecules promoted from vibrationally excited and vibrationless ground states confirmed that the FC factors and not the ensuing dynamics are the main reason for the mode specificity in this molecule.
View Article and Find Full Text PDFPhys Chem Chem Phys
July 2015
Department of Physics, Ben-Gurion University of the Negev, Beer-Sheva 84105, Israel.
Non-adiabatic dynamics at conical intersections (CIs) extensively affects the photostability of biomolecules by efficiently photoinducing decay routes that dissipate harmful excess ultraviolet energy. Here the predissociation of the model test molecules, methylamine (CH3NH2) and its partially deuterated isotopologue (CD3NH2), excited to different specific vibrational modes in the electronically excited state has been experimentally investigated. The H(D) photofragments were detected by two-color reduced-Doppler ion imaging, which allows measurement of their entire velocity distributions in each laser pulse.
View Article and Find Full Text PDFJ Chem Phys
November 2013
Department of Physics, Ben-Gurion University of the Negev, Beer-Sheva 84105, Israel.
Two-color reduced-Doppler (TCRD) and one-color velocity map imaging (VMI) were used for probing H atom photofragments resulting from the ~243.1 nm photodissociation of pyrrole. The velocity components of the H photofragments were probed by employing two counterpropagating beams at close and fixed wavelengths of 243.
View Article and Find Full Text PDFJ Chem Phys
April 2011
Department of Chemistry, Wayne State University, Detroit, Michigan 48202, USA.
We present a direct current slice imaging study of tetrachloroethylene (C(2)Cl(4)) photodissociation, probing the resulting ground state Cl ((2)P(3/2)) and spin-orbit excited state Cl* ((2)P(1/2)) products. We report photofragment images, total translational energy distributions and the product branching ratio of Cl*/Cl following dissociation at 235 and 202 nm, obtained using a two-color reduced-Doppler dissociation/probe. Near 235 nm, the Cl translational energy distribution shows a peak at the limit of the available energy, indicating a direct dissociation through a σ*(C-Cl) ← π (C=C) transition, which is superimposed on a broader underlying distribution.
View Article and Find Full Text PDFProc Natl Acad Sci U S A
September 2008
Department of Chemistry, Wayne State University, Detroit, MI 48202, USA.
We present an experimental investigation of the UV photochemistry of diacetylene under collisionless conditions. The H loss channel is studied using DC slice ion imaging with two-color reduced-Doppler detection at 243 nm and 212 nm. The photochemistry is further studied deep in the vacuum UV, that is, at Lyman-alpha (121.
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