A vector correlation study using a hexapole-oriented molecular beam: photodissociation dynamics of oriented isohaloethane.

The photodissociation dynamics of isohaloethane (1-bromo-2-chloro-1,1,2-trifluoroethane) at 234 nm was studied by a sliced imaging technique combined with an oriented molecular beam. The speed and angular distributions of the competitive products of spin-orbit selected Br and Cl atoms were determined by analysis of the obtained images. The anisotropic parameter, ß, was found to be 2.0 ± 0.2 for the excited state of Br(2P1/2) (Br*) and 1.2 ± 0.3 for the ground state of Br(2P3/2) (Br). The speed distributions for both Br and Br* exhibited Gaussian-like characteristics. These results indicate that Br atoms were generated by direct formation after excitation through the nσ*(C-Br) potential energy surfaces. In contrast, the angular distributions for the Cl fragments were almost isotropic, while the speed distributions displayed Boltzmann-like characteristics. This suggests that the Cl atoms may form through long-lived parent molecules after photoexcitation. The branching ratio for Br and Cl atom formation was found to be approximately 1.2, that is, Br atom formation occurred preferentially, in contrast to the case of halothane photodissociation reported in our previous work [Che et al., J. Phys. Chem. A, 2020, 124, 5288]. A vector correlation study between the laser polarization axis and the direction of the dipole moment revealed a similar tendency for all photofragments, suggesting that the fragments were formed through a common excited state of isohaloethane. The vector correlation was also studied theoretically for comparison with the experimental results. The angle between the transition dipole moment in photodissociation and the permanent dipole moment was found to be 42 ± 15°. The obtained results indicate that this vector correlation approach combined with an oriented molecular beam is a powerful tool for determining the transition dipole moments in photodissociation.

Photodissociation Dynamics of CF2ClCHFI Using Slice Imaging Combined with a Hexapole-Oriented Molecular Beam.

Photodissociation dynamics of 1-chloro-2-iodo-1,1,2-trifluoroethane (CF2ClCHFI) were investigated at 267 nm by a slice imaging technique combined with an oriented molecular beam. The speed and angular distributions of the spin-orbit-selected I atoms were determined by analyzing the images. The anisotropic parameter was 1.67 ± 0.04 for the ground state of I(2P3/2) and 1.94 ± 0.04 for the excited state of I(2P1/2). A vector correlation study between the laser polarization and the dipole moment of the molecule revealed that the transition dipole moment in photoabsorption was found to be at 90° ± 15 to the molecular dipole moment, suggesting the transition dipole moment was nearly parallel to the C-I bond axis. The quantum yield for the excited state obtained from the observed signal intensities was estimated to more than 0.9 at this wavelength. The analysis of the kinetic energy release for both fragments indicated that a large amount of energy was distributed into the internal energy of the CF2ClCHF· radical, which led to the secondary reaction of the C-Cl bond rupture. The study of the ground state of Cl atom formation via photolysis at 235 nm supported the existence of the secondary reaction. The results of the kinetic energy release of the I photofragments and the analysis of the image for the photofragment of the Cl atom suggested that the ground state of I atom formation mainly led to the secondary reaction of the C-Cl bond rupture through the short-lived CF2ClCHF· radical. However, only part of the excited state of I atom formation involved the Cl atom formation through the long-lived CF2ClCHF· radical.

UV Photodissociation of Halothane in a Focused Molecular Beam: Space-Speed Slice Imaging of Competitive Bond Breaking into Spin-Orbit-Selected Chlorine and Bromine Atoms.

A molecular beam of halothane (2-bromo-2-chloro-1,1,1-trifluoroethane) is focused by a hexapolar electrostatic field and photolyzed by UV laser radiation at 234 nm. Angular and speed distributions of chlorine and bromine photofragments emitted from halothane are measured for both spin-orbit states independently. Although the dissociation energy of the C-Cl bond is larger than that of C-Br, the relative yield of Cl to Br was found to be approximately 2. Measured speed and angular distributions of atomic fragments show distinct kinetic energy release and scattering characteristics: for bromine, observed fast and aligned fragments exhibit a signature of a direct mode of dissociation for the C-Br bond, via the electronically excited potential energy surface denoted nσ*(C-Br), of repulsive nature; for chlorine, a variation in the features is observed for the dissociation pathway through nσ*(C-Cl), from a modality similar to the bromine case, leading to fragments with appreciable kinetic energy release and pronounced directionality, to a modality involving slow products, nearly isotopically distributed. The origin of this behavior can be attributed to nonadiabatic interaction operating between the nσ*(C-Br) and nσ*(C-Cl) surfaces. These results are not only relevant for a detailed understanding of adiabatic versus diabatic coupling mechanisms in the manifold of excited states populated by photon absorption, but they also point out the possibility of selectively inducing specific dissociation pathways, even when involving energetically unfavorable outcomes, such as, in this case, the prevailing rupture of the stronger C-Cl bond against that of the weaker C-Br bond.

Atomic force microscopy analysis of SasA-KaiC complex formation involved in information transfer from the KaiABC clock machinery to the output pathway in cyanobacteria.

The cyanobacterial clock oscillator is composed of three clock proteins: KaiA, KaiB and KaiC. SasA, a KaiC-binding EnvZ-like orthodox histidine kinase involved in the main clock output pathway, exists mainly as a trimer (SasA3mer ) and occasionally as a hexamer (SasA6mer ) in vitro. Previously, the molecular mass of the SasA-KaiCDD complex, where KaiCDD is a mutant KaiC with two Asp substitutions at the two phosphorylation sites, has been estimated by gel-filtration chromatography to be larger than 670 kDa. This value disagrees with the theoretical estimation of 480 kDa for a SasA3mer -KaiC hexamer (KaiC6mer ) complex with a 1:1 molecular ratio. To clarify the structure of the SasA-KaiC complex, we analyzed KaiCDD with 0.1 mmol/L ATP and 5 mmol/L MgCl2 (Mg-ATP), SasA and a mixture containing SasA and KaiCDD6mer with Mg-ATP by atomic force microscopy (AFM). KaiCDD images were classified into two types with height distribution corresponding to KaiCDD monomer (KaiCDD1mer ) and KaiCDD6mer , respectively. SasA images were classified into two types with height corresponding to SasA3mer and SasA6mer , respectively. The AFM images of the SasA-KaiCDD mixture indicated not only KaiCDD1mer , KaiCDD6mer , SasA3mer and SasA6mer , but also wider area "islands," suggesting the presence of a polymerized form of the SasA-KaiCDD complex.

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 µ, 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) photofragments were acquired at 234.0 and 254.1 nm, respectively, by a (2 + 1) resonance-enhanced multiphoton ionization technique. A detailed analysis of the sliced ion images obtained at a tilting angle 45° of laser polarization provides information on the correlation of the three vectors, which are confined by two polar angles α and χ and one azimuthal angle φµd in the recoil frame. The sliced ion images of Br fragments eliminated individually from the enantiomers at 254.1 nm yield an asymmetric factor close to zero; for this reason the photofragment angular distributions do not show significant differences. The elimination of the 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° and 164° ± 1° for α and χ, respectively, whereas φµd is approaching 0° for the best fit. Since for the present molecule, the three vectors have an only slight spatial arrangement, the photofragment angular distributions of the two enantiomers do not show appreciable differences. Theoretical and computational simulations provide us the basis to state that oriented enantiomers can be discriminated on-the-fly in photodissociation processes even initiated by non-circularly polarized light, provided that the three vectors encountered above have specific three-dimensional arrangements. The fact that Br fragment elimination involves a multi-potential dissociation carries uncertainties in theoretical estimates of the vector direction. Therefore, this work represents a preliminary but significant step on the road to chiral discrimination on-the-fly, which is shown to be best propitiated in molecules where vectors are far from having degenerate mutual angular directions.

Stereodynamic Imaging of Bromine Atomic Photofragments Eliminated from 1-Bromo-2-methylbutane Oriented via Hexapole State Selector.

Both single-laser and two-laser experiments were conducted to look into the ion-imaging of Br*(2P1/2) and Br(2P3/2) photofragmented from 1-bromo-2-methylbutane in the range 232-240 nm via a detection scheme of (2+1) resonance-enhanced multiphoton ionization. The angular analysis of these photofragment distributions yields the anisotropy parameter ß = 1.88 ± 0.06 for the Br* excited state which arises from a parallel transition, while ß = 0.63 ± 0.09 for the Br ground state indicates the contribution from both a perpendicular transition and a non-adiabatic transition. When a hexapole coupled with an orienting field was implemented, the parent molecules are spatially oriented to yield an orientation efficiency |⟨cos Î¸⟩| of 0.15. Besides the χ angle between the recoil velocity v and the transition dipole moment µ, orienting molecules allows for the evaluation of the angle α between v and the permanent molecular dipole moment d. The angular analysis of Br* photofragment distribution yields χ = 11.5° and α in the range from 160° to 180° with weak dependency. In the two-laser experiments, the angular anisotropy of Br photofragment distribution was found to be smaller (0.38 ± 0.10) when the photolysis wavelength was red-shifted to 240 nm, suggesting the increasing contributions from perpendicular transitions.

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 ß1 of 0.67, indicative of the extent of molecular orientation, and an anisotropy parameter ß2 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 (ß1 = 0.24) and the obtained small value ß2 = 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.

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.

Control of conformers combining cooling by supersonic expansion of seeded molecular beams with hexapole selection and alignment: experiment and theory on 2-butanol.

Selection and alignment of rotamers and, more in general, of conformers in the gas phase is a challenge that we tackle experimentally by supersonic expansion of seeded molecular beams and hexapolar electrostatic fields with quadrupole mass detection. The studied system involves the nine conformers of the asymmetric-top molecule 2-butanol, which coexist because of nearly free rotations around a CC and a CO bond. From the measured time-of-flight of a 2-butanol supersonic molecular beam seeded in either He or Ar, the corresponding velocity distributions are obtained. The different nature and masses of the seeding gas decrease selectively the vibrational temperature and determine the population of the conformers, which is assessed on the basis of their statistical distribution, derived from high level accompanying quantum mechanical calculations. The use of a hexapolar electrostatic field permits us to induce a variation of the population distribution as a function of the applied voltage and of the selective focusing and alignment of the conformers. A technique, recently developed for treating asymmetric tops and involving extensive trajectory simulations, is applied to obtain the link between the focusing curves, i.e. the dependence of the beam intensity on the hexapole voltage, and the conformers' populations and alignment. Perspectives are provided for photo- and stereo-dynamics experiments, particularly appealing also on account that 2-butanol is the simplest chiral alcohol.

Directions of chemical change: experimental characterization of the stereodynamics of photodissociation and reactive processes.

This perspective article aims at accounting for the versatility of some current experimental investigations for exploring novel paths in chemical reactions. It updates a previous one [Phys. Chem. Chem. Phys., 2005, 5, 291] and is limited to work by the authors. The use of advanced molecular beam techniques together with a combination of modern tools for specific preparation, selection and detection permits us to discover new trends in reactivity in the gas phase as well as at interfaces. We specifically discuss new facets of stereodynamics, namely the effects of molecular orientation and alignment on reactive and photodissociation processes. Further topics involve roaming paths and triple fragmentation in photodissociation probed by imaging techniques, chirality effects in collisions and deviations from Arrhenius behavior in the temperature dependence of chemical reactions.

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.

Molecular hydrogen consumption in the human body during the inhalation of hydrogen gas.

Inhaling or ingesting hydrogen (H2) gas improves oxidative stress-induced damage in animal models and humans. We previously reported that H2 was consumed throughout the human body after the ingestion of H2-rich water and that the H2 consumption rate ([Formula: see text]) was 1.0 µmol/min/m(2) body surface area. To confirm this result, we evaluated [Formula: see text]during the inhalation of low levels of H2 gas. After measuring the baseline levels of exhaled H2 during room air breathing via a one-way valve and a mouthpiece, the subject breathed low levels (160 ppm) of H2 gas mixed with purified artificial air. The H2 levels of their inspired and expired breath were measured by gas chromatography using a semiconductor sensor. [Formula: see text] was calculated using a ventilation equation derived from the inspired and expired concentrations of O2/CO2/H2, and the expired minute ventilation volume, which was measured with a respiromonitor. As a result, [Formula: see text] was found to be approximately 0.7 µmol/min/m(2)BSA, which was compatible with the findings we obtained using H2-rich water. [Formula: see text] varied markedly when pretreatment fasting to reduce colonic fermentation was not employed, i.e., when the subject's baseline breath hydrogen level was 10 ppm or greater. Our H2 inhalation method might be useful for the noninvasive monitoring of hydroxyl radical production in the human body.

Orientation dependence for Br formation in the reaction of oriented OH radical with HBr molecule.

The orientation dependence of Br-atom formation in the reaction of the oriented OH radical with the HBr molecule using the hexapole electrostatic field was studied. Experimental results for the orientation dependence in the reaction were analyzed using a Legendre polynomial fit. The results show two reactive sites. It was found that O-end attack is most favored for this reaction, and that H-end attack also shows a pronounced reactivity. The reactivity of the side-ways attack was found to be small. By comparing the results of the orientation dependence in the reaction with studies of inelastic collisions and theoretical calculations, two reaction pathways are proposed. Reaction by O-end attack is followed by a direct abstraction of the H-atom from the HBr molecule. The mechanism for H-end attack may have H-atom migration from HBr to form the water molecule.

Orientation dependence in the four-atom reaction of OH + HBr using the single-state oriented OH radical beam.

The orientation dependence for the Br atom formation in the reaction of the oriented OH radicals with HBr molecules at 0.26 eV collision energy has been observed for the first time using the hexapole electric field, and we found that the reaction cross-section for O-end attack is more favorable than that for H-end attack by a factor of 3.4 +/- 2.3.

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.

Negative collision energy dependence of Br formation in the OH + HBr reaction.

The reaction between HBr and OH leading to H(2)O and Br in its ground state is studied by means of a crossed molecular beam experiment for a collision energy varying from 0.05 to 0.26 eV, the initial OH being selected in the state |JOmega> = |3/2 3/2> by an electrostatic hexapole field. The reaction cross-section is found to decrease with increasing collision energy. This negative dependence suggests that there is no barrier on the potential energy surface for the formation pathway considered. The experimental results are compared with the previously reported quantum scattering calculations of Clary et al. (D. C. Clary, G. Nyman and R. Hernandez, J. Phys. Chem., 1994, 101, 3704), and briefly discussed in the light of skewed potential energy surfaces associated with heavy-light-heavy type reactions.