Dock-Chil Che

Electrostatic Hexapole State-Selection of the Asymmetric-Top Molecule Propylene Oxide†

Rotational state-selection of the asymmetric-top molecule propylene oxide was carried out using an electrostatic hexapole field of 85-cm length. Molecular beam intensities were monitored by a quadrupole mass spectrometer. It was found that beam intensities of molecular beams for pure propylene oxide and those seeded in He and in Ar increased with increasing hexapole voltages. The hexapole voltage dependence of the beam intensity, which is called the focusing curve, was interpreted by computer simulation of the trajectories of molecules in the hexapolar field due to the Stark effect, as a function of rotational temperatures of molecular beams. The calculated best fit focusing curves, when compared with the experimental results, demonstrated that the rotational temperatures, associated with the distribution of states of a given rotational angular momentum J, are similar to the translational temperatures. It was found that the M = 0 states (where M is the projection of J along the direction of the electrostatic field) and negative values of the pseudoquantum number tau of propylene oxide can be selected using our experimental setup. These results suggest that the hexapole electric field is a tool even for the selection of rotational and orientation states of asymmetric-top molecules.

Aligned molecules: chirality discrimination in photodissociation and in molecular dynamics

Emergence of biochemical homochirality is an intriguing topic, and none of the proposed scenarios has encountered a unanimous consensus. Candidates for naturally occurring processes, which may originate chiral selection, involve interaction of matter with light and molecular collisions. We performed and report here: (1) simulations of photodissociation of an oriented chiral molecule by linearly polarized (achiral) light observing that the angular distribution of the photofragments is characteristic of each enantiomer and both differ from the racemic mixture; and (2) molecular dynamics simulations (elastic collisions of oriented hydrogen peroxide, one of the most simple chiral molecules, with Ne atom) demonstrating that the scattering and the recoil angles are specific of the enantiomeric form. The efficacy of non-chiral light (in the case of photodissociation) and of non-chiral projectile (in the case of collisions) is due to the molecular orientation, as an essential requirement to observe chiral effects. The results of the simulations, that we report in this article, provide the background for the perspective realization of experiments which go beyond the well-documented ones involving interaction of circularly polarized laser (chiral light) with the matter, specifically by making use of non-chiral, i.e. linearly polarized or unpolarized light sources, and also by obtaining chiral effects with no use at all of light, but simply inducing them by molecular collisions. The case of vortices is discussed in a companion paper.

Single |JΩMJ〉 state-selection of OH radicals using an electrostatic hexapole field

The focusing curve of the single quantum state |JΩMJ〉 = |1/2,1/2,1/2〉 of OH radicals was measured using the combined methods of state selection with an electrostatic hexapole of 1 m length, and detection by laser induced fluorescence for the OH(A ← X) transition at 308 nm. The observed focusing curve is a reliable test for the trajectory simulation since it only consists out of a single quantum state of molecules. The trajectory simulations including the Λ-type doubling effect could reproduce the observed focusing curves. The focusing curves for |JΩ> = |3/2,3/2〉, |5/2,3/2〉, and |7/2,3/2〉 were also measured. The results were compared with the trajectory simulations and discussed with the population of the contributed |MJ| states in the focusing curves.

Collision energy dependence for the Br formation in the reaction of OD+HBr

The collision energy dependence for Br(2P3/2) atom formation in the reaction of OD + HBr has been investigated from 0.05 to 0.26 eV using a crossed molecular beam experiment. OD radicals were selected as the single rotational state in the upper state of Λ-doubling of using a 1 m electric hexapole field. Br atoms were detected by the vacuum ultraviolet (VUV) laser-induced fluorescence technique. We find that the reaction cross-section decreases, increasing the collision energy. This negative collision energy dependence suggests that there is no barrier on the potential energy surface for the formation pathway considered. Results were compared with those previously reported for the OH + HBr reaction system. We find that the ratio of the reaction cross-section of σ(OD)/σ(OH) shows values larger than one and an increasing tendency when collision energy increases. The collision energy dependence observed is explained in terms of the zero-point energy differences and the rotational periods of OD and OH, which may be related to the time for the proper reorientation of the OH radical prior to the reaction.

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 past 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 the 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), was successfully oriented by a weak homogeneous field placed downstream from the hexapolar filter. Efficiency of the orientation was 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 ((2)P3/2) and the excited Br ((2)P1/2) 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 nonoriented molecules.

Stereodirectional images of molecules oriented by a variable-voltage hexapolar field: Fragmentation channels of 2-bromobutane electronically excited at two photolysis wavelengths

The asymmetric-top molecule 2-bromobutane is oriented by means of a hexapole state selector; the angular distribution of the bromine atom photofragment, for the two fine-structure components, is acquired by velocity-map ion imaging. The molecular beam, spatially oriented along the time-of-flight axis, is intersected with a linearly polarized laser, whose polarization is tilted by 45° with respect to the detector surface. To obtain the mixing ratio of the perpendicular and parallel transitions, the fragment ion images and angular distributions can be appropriately simulated to give insight on the population mechanism of the specific electronic state involved at each selected excitation wavelength. The photofragment images obtained at 238.6 nm yielded an asymmetry factor β1 of 0.67, indicative of the extent of molecular orientation, and an anisotropy parameter β2 of 1.03, which is a signature of a prevailing parallel transition along the C-Br axis. When the photolysis wavelength is tuned to 254.1 nm, the corresponding angular distribution is less asymmetric (β1 = 0.24) and the obtained small value β2 = 0.12 is a characteristic of a predominantly perpendicular transition. The photofragment angular distributions are also affected by hexapole voltage, especially regarding the asymmetry factor, and this aspect provides information on the effect of molecular orientation.

Alignment selection of the metastable CO(a 3Π1) molecule and the steric effect in the aligned CO(a 3Π1) + NO collision.

The aligned metastable CO(a (3)Π1) molecular beam was generated by an electronic excitation through the Cameron band (CO a (3)Π1 ← X (1)Σ(+)) transition. Beam characterization of the aligned molecular beam of CO(a (3)Π1) was carried out by (1 + 1) REMPI detection via the b (3)Σ(+) state. The REMPI signals showed the clear dependence on the polarization of the pump laser, and the experimental result was well reproduced by the theoretical simulation. This agreement confirms that aligned metastable CO(a (3)Π1) can be generated and controlled by rotating polarization of the pump laser. By using this technique, a single quantum state of CO(a (3)Π1) can be selected as a metastable molecular beam. The steric effect in the energy-transfer collision of CO(a (3)Π1) with NO forming the excited NO was carried out with this aligned CO(a (3)Π1) molecular beam. We find that the sideways orientation of CO(a (3)Π1) is more favorable in the formation of the excited NO(A (2)Σ(+), B (2)Π) than that for the axial collisions. The obtained steric effect was discussed with the aid of the spatial distribution of CO(a (3)Π1) molecular orbitals, and we find that specific rotational motion of CO(a (3)Π1) in each state may not be a dominant factor in this energy-transfer collision.

Photodissociation of DCl dimer selected by an electrostatic hexapole field combined with a Doppler-selected time-of-flight technique: observation of [ClDCl] transient species

The photodissociation of the DCl dimer, which was preferentially selected from the cluster beam using a hexapole electrostatic field prior to the photolysis, was studied by a Doppler-selected time-of-flight (DS-TOF) technique at 243 nm. We observed the [ClDCl] transient product after deuterium elimination from (DCl)2. By measuring the dependence of the enhanced signal for the photodissociated D atom on the hexapole voltage, it was found that the DS-TOF spectrum is composed of two kinds of velocity component: one is a fast velocity component which originates from the dimer only, and the other is a slow velocity component which originates not only from the dimer but also from higher DCl cluster sizes. The fast velocity component of the spectrum shows oscillating structures, which may be an indication of the nascent internal (mainly vibrational) state of [ClDCl]. The spacing of the peaks is about 800 cm−1, which is less than half of the normal stretching frequency of the DCl monomer (i.e. 2091 cm−1). Therefore, we tentatively conclude that the present spectrum exhibits strong perturbation by the adjacent Cl atom in the [ClDCl] transient species.

Stereodynamics: From elementary processes to macroscopic chemical reactions

This paper aims at discussing new facets on stereodynamical behaviors in chemical reactions, i.e. the effects of molecular orientation and alignment on reactive processes. Further topics on macroscopic processes involving deviations from Arrhenius behavior in the temperature dependence of chemical reactions and chirality effects in collisions are also discussed.

Nanoscale charge transport in cytochrome c3/DNA network: Comparative studies between redox-active molecules

The redox-active molecule of a cytochrome c3/DNA network exhibits nonlinear current–voltage (I–V) characteristics with a threshold bias voltage at low temperature and zero-bias conductance at room temperature. I–V curves for the cytochrome c3/DNA network are well matched with the Coulomb blockade network model. Comparative studies of the Mn12 cluster, cytochrome c, and cytochrome c3, which have a wide variety of redox potentials, indicate no difference in charge transport, which suggests that the conduction mechanism is not directly related to the redox states. The charge transport mechanism has been discussed in terms of the newly-formed electronic energy states near the Fermi level, induced by the ionic interaction between redox-active molecules with the DNA network.