SearcharxivSearch

arXiv subjects

Po-Yu Tsai

Publications and source records attributed to Po-Yu Tsai.

4 recordsLinked to original sources

Vectorial Imaging of the Photodissociation of 2-Bromobutane Oriented via Hexapolar State Selection

Molecular orientation techniques are becoming available in the study of elementary chemical processes, in order to highlight those structural and dynamical properties that would be concealed by random rotational motions. Recently successful orientation was achieved for asymmetric-top and chiral molecules of much larger complexity than hitherto. In this work, we report and discuss the correlation between the vectors photofragment recoil velocity v, transition dipole moment {\mu}, and permanent dipole moment d in a dissociation experiment on hexapole oriented 2-bromobutane, photoinitiated by a linearly polarized laser. The sliced ion images of the Br* (2P1/2) and Br (2P3/2) photofragment were acquired at 234.0 and 254.1 nm, respectively, by (2+1) resonance-enhanced multiphoton ionization technique. A detailed analysis of the sliced ion images obtained at a tilting angle 45o of the laser polarization provides the information on correlation of the three vectors, which are confined by two polar angles {\alpha}, \c{hi} and one azimuthal angle {\phi}{\mu}d in the recoil frame. The sliced ion images of Br fragments eliminated individually from the enantiomers at 254.1 nm yield the asymmetric factor close to zero; for this reason the photofragment angular distributions do not show significant differences. The elimination of Br* fragment at 234.0 nm is mainly correlated with a parallel transition, giving rise to a large anisotropy parameter of 1.85, and thus can be considered as a single state excitation. The resulting recoil frame angles are optimized to 163.8{\deg} and 164.1{\deg} for {\alpha} and \c{hi}, respectively, whereas {\phi}{\mu}d approaches close to 0o for the best fit. Since in the present case, the three vectors have an only slight spatial arrangement, the photofragment angular distributions of the two enantiomers do not show appreciable differences...

physics.chem-ph

Hexapole-Oriented Asymmetric-Top Molecules and Their Stereodirectional Photodissociation Dynamics

Molecular orientation is a fundamental requisite in the study of stereodirected dynamics of collisional and photoinitiated processes. In this last decade, variable hexapolar electric filters have been developed and employed for the rotational-state selection and the alignment of molecules of increasing complexity, for which main difficulties are their mass, their low symmetry and the very dense rotational manifold. In this work, for the first time, a complex molecule such as 2-bromobutane, an asymmetric-top containing a heavy atom (the bromine), has been successfully oriented by a weak homogeneous field placed downstream the hexapolar filter. Efficiency of the orientation has been characterized experimentally, by combining time-of-flight measurements and a slice-ion-imaging detection technique. The application is described to the photodissociation dynamics of the oriented 2-bromobutane, which was carried out at a laser wavelength of 234 nm, corresponding to the breaking of the C Br bond. The Br photofragment is produced in both the ground Br (2P3/2) and the excited Br (2P1/2) electronic states and both channels are studied by the slice imaging technique, revealing new features in the velocity and angular distributions with respect to previous investigations on non-oriented molecules.

physics.chem-ph

Stereodirectional Photodynamics: Experimental and Theoretical Perspectives

Hexapole oriented 2-bromobutane is photodissociated and detected by a slice ion imaging technique at 234 nm. The laser wavelength corresponds to the C Br bond breaking with emission of a Br atom fragment in two accessible fine structure states: the ground state Br and the excited state Br*, both observable separately by resonance enhanced multiphoton ionization (REMPI). Orientation is evaluated by time of flight measurements combined with slice ion imaging.

physics.chem-ph

Rotational state-selection and alignment of chiral molecules by electrostatic hexapoles

Electrostatic hexapoles are revealed as a powerful tool in the rotational state-selection and alignment of molecules to be utilized in beam experiments on collisional and photoinitiated processes. In the paper, we report results on the application of the hexapolar technique on the recently studied chiral molecules propylene oxide, 2-butanol and 2bromobutane, to be investigated in selective photodissociation and enantiomeric discrimination.

physics.chem-ph