Pulsed-laser production and detection of spin-polarized hydrogen atoms.

Spin-polarized hydrogen (SPH) atoms have traditionally been produced and detected using complex experimental methods with poor time resolution. Recently, SPH has been produced by pulsed-laser photodissociation of HCl using circularly polarized light. In combination with the proposed detection of SPH via polarized fluorescence, this approach should allow the production and spatially resolved detection of SPH with a higher sensitivity than that currently available, and with a time resolution in the nanosecond regime. This represents an improvement of several orders of magnitude over the existing methods.     

Analysis of collisional alignment and orientation studied by scattering of spin-polarized electrons from laser excited atoms

A general framework using density matrices is developed for the analysis of atomic excitation by spin-polarized electrons. This framework is applied to the specific case of the 3S _1/2→3P _3/2 transition in Na, as studied by the time-reversed, superelastic process. The scattering is characterized in terms of physical parameters describing the collisionally excitedp-state, i.e., its angular momentum (L _⊥), linear polarization (P _lin), and alignment angle (γ), with these parameters defined separately for singlet and triplet excitation. An expression for the scattering intensity is derived which is valid for arbitrary electron polarization and atomic state preparation. Specific examples are discussed with a view toward complete determination of the relevant scattering amplitudes and phases. Recent experimental results are reevaluated for comparison with theoretical calculations, and suggestions are made for future experiments.     

Molecular photofragment orientation in the photodissociation of H2O2 at 193 nm and 248 nm

Angular momentum orientation has been observed in the OH(X(2)Π, v = 0) fragments generated by circularly polarized photodissociation of H(2)O(2) at 193 nm and 248 nm. The magnitude and sign of the orientation are strongly dependent on the OH(X) photofragment rotational state. In addition to conventional laser induced fluorescence methods, Zeeman quantum beat spectroscopy has also been used as a complementary tool to probe the angular momentum orientation parameters. The measured orientation at 193 nm is attributed solely to photodissociation via the ?(1)A state, even though at this wavelength H(2)O(2) is excited near equally to both the ?(1)A and B(1)B electronic states. This observation is confirmed by measurements of the photofragment orientation at 248 nm, where access to the ?(1)A state dominates. Several possible mechanisms are discussed to explain the observed photofragment orientation, and a simple physical model is developed, which includes the effects of the polarization of the parent molecular rotation upon absorption of circularly polarized light. Good agreement between the experimental and simulation results is obtained, lending support to the validity of the model. It is proposed that photofragment orientation arises mainly from the coupling of the parent rotational angular momentum with that induced during photofragmentation.     

(2+1) laser-induced fluorescence of spin-polarized hydrogen atoms

We report the measurement of the spin polarization of hydrogen (SPH) atoms by (2+1) laser-induced fluorescence, produced via the photodissociation of thermal HBr molecules with circularly polarized 193 nm light. This scheme, which involves two-photon laser excitation at 205 nm and fluorescence at 656 nm, offers an experimentally simpler polarization-detection method than the previously reported vacuum ultraviolet detection scheme, allowing the detection of SPH atoms to be performed more straightforwardly, from the photodissociation of a wide range of molecules and from a variety of collision experiments.     

Two-photon state selection and angular momentum polarization probed by velocity map imaging: application to H atom photofragment angular distributions from the photodissociation of two-photon state selected HCl and HBr

A formalism for calculating the angular momentum polarization of an atom or a molecule following two-photon excitation of a J-selected state is presented. This formalism is used to interpret the H atom photofragment angular distributions from single-photon dissociation of two-photon rovibronically state selected HCl and HBr prepared via a Q-branch transition. By comparison of the angular distributions measured using the velocity map imaging technique with the theoretical model it is shown that single-photon dissociation of two-photon prepared states can be used for pathway identification, allowing for the identification of the virtual state symmetry in the two-photon absorption and/or the symmetry of the dissociative state. It is also shown that under conditions of excitation with circularly polarized light, or for excitation via non-Q-branch transitions with linearly polarized light the angular momentum polarization is independent of the dynamics of the two-photon transition and analytically computable.     

Microwave ionization of highly excited hydrogen atoms

Within a 1-dimensional model we calculate quantum mechanically the probability to ionize a highly excited hydrogen atom by a monochromatic microwave field. Based on a detailed analysis of the ionization process we developed a computational scheme as well as a simple physical framework which are presented and discussed. Our calculations are in good agreement with the experimental results. We show that the experimentally measured ionization thresholds are due to a sharp transition between two localization regimes and that recently measured structures below the classical chaos border are due to unresolved clusters of Floquet pseudo crossings. We propose an experimental method by which one could measure the distance and distribution of crossing Floquet eigenvalues.     

Extracting the polarizability anisotropy from the transient alignment of HBr

We use 40 fs, 780 nm laser pulses to transiently align HBr molecules. We study the temporal dynamics of the resultant rotational wavepacket to gain insight into the electronic properties of the molecule. We show that the HBr polarization anisotropy can be extracted by comparing the time dependence of the HBr alignment with both the analogous alignment behavior of N(2) and the predictions of a rigid-rotor model.     

Branching ratios for BrO production from reactions of O(1D) with HBr,CF3Br,CH3Br,CF2ClBr,and CF2HBr

Laser-flash photolysis of RBr/O₃/SF₆/He mixtures at 248 nm has been coupled with BrO detection by time-resolved UV absorption spectroscopy to measure BrO product yields from O(¹D) reactions with HBr, CF₃Br, CH₃Br, CF₂ClBr, and CF₂HBr at 298±3 K. The measured yields are: HBr, 0.20±0.04; CF₃Br, 0.49±0.07; CH₃Br, 0.44±0.05; CF₂ClBr, 0.31±0.06; and CF₂HBr, 0.39±0.07 (uncertainties are 2σ and include estimates of both random and systematic errors). The results are discussed in light of other available information or O(¹D)+RBr reactions. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 555–563, 1998     

Elimination of HBr from CH3Br by Cu＋ and Au＋： A DFT study

The elimination of HBr from CH3Br by ground state of Cu＋ and Au＋ has been investigated by using DFT methods. A mechanism of one-step HBr elimination leading to CuCH2＋ was identified. For the formation of AuCH2＋, besides the one-step mechanism, another two-step HBr elimination pathway through a C-Br bond insertion intermediate was also found, and this pathway is energetically more favorable than the one-step mechanism. The calculated reaction energy barriers show that the formation of AuCH2＋ is energetically much more favorable than the formation of CuCH2＋. The experimental observations are well explained.     

Polarization of thallium atoms produced in molecular photodissociation: experiment and theory

A study has been made of the oriented ground state Tl(6² P _1/2) atoms produced in the photodissociation of TlBr molecules by circularly polarized 266-nm laser light. A significant degree of atomic orientation (15%) has been measured in the experiment which corresponds to the initial degree of orientation of 37%. A high value of depolarization cross section (210 Ų) for the oriented Tl atoms colliding with TlBr molecules has been also observed. The obtained experimental results have been treated theoretically. We present a general quantum mechanical theory of the orientation phenomenon in which all possible nonadiabatic interactions as well as molecular rotation are properly treated. The application of the theory to the case of TlBr photodissociation allowed to understand the obtained experimental results and to evaluate the probability of the earlier unknown radial nonadiabatic transition in the decaying molecule.     

Photofragment alignment in the photodissociation of I2 from 450 to 510 nm

A combination of velocity map imaging and slicing techniques have been used to measure the product recoil anisotropy and angular momentum polarization for the photodissociation process I2-->I(2P(3/2))+I(2P(3/2)) and I2-->I(2P(3/2)))+I(2P(1/2)) in the 450-510 nm laser wavelength region using linearly polarized photolysis and probe laser light. The former channel is produced predominantly via perpendicular excitation to the 1Piu state, and the latter is predominantly parallel, via the B 3Pi(0u)+ state. In both cases we observe mostly adiabatic dissociation, which produces electronically aligned iodine atoms in the mid /m/=1/2 states with respect to the recoil direction.     

Influence of electron and nuclear spin on photofragment alignment: Application to CICN dissociation at 157.6 nm

The alignment determined from rotationally resolved CN emission following CICN photodissociation does not describe the quadrupole moment of the nuclear     

A feasibility study of75Br and77Br production from enriched krypton

Methods for the production of radiochemically pure bromine radionuclides were studied. Enriched target material yields were calculated from measurements based on experiments performed with non-enriched target gas. A special target system is to be developed.     

Photodissociation of HBr. 1. Electronic structure, photodissociation dynamics, and vector correlation coefficients

Ab initio potential energy curves, transition dipole moments, and spin-orbit coupling matrix elements are computed for HBr. These are then used, within the framework of time-dependent quantum-mechanical wave-packet calculations, to study the photodissociation dynamics of the molecule. Total and partial integral cross sections, the branching fraction for the formation of excited-state bromine atoms Br(2P(1/2)), and the lowest order anisotropy parameters, beta, for both ground and excited-state bromine are calculated as a function of photolysis energy and compared to experimental and theoretical data determined previously. Higher order anisotropy parameters are computed for the first time for HBr and compared to recent experimental measurements. A new expression for the Re[a1(3) (parallel, perpendicular)] parameter describing coherent parallel and perpendicular production of ground-state bromine in terms of the dynamical functions is given. Although good agreement is obtained between the theoretical predictions and the experimental measurements, the discrepancies are analyzed to establish how improvements might be achieved. Insight is obtained into the nonadiabatic dynamics by comparing the results of diabatic and fully adiabatic calculations.     

Electrochemical catalytic reforming of oxygenated-organic compounds: a highly efficient method for production of hydrogen from bio-oil

A novel approach to produce hydrogen from bio-oil was obtained with high carbon conversion (>90%) and hydrogen yield (>90%) at T<500 degrees C by using the electrochemical catalytic reforming of oxygenated-organic compounds over 18%NiO/Al(2)O(3) reforming catalyst; thermal electrons play important promoting roles in the decomposition and reforming of the oxygenated-organic compounds in the bio-oil.     

Optical control of ground-state atomic orbital alignment: Cl(2P3/2) atoms from HCl(v=2,J=1) photodissociation

H(35)Cl(v=0,J=0) molecules in a supersonic expansion were excited to the H(35)Cl(v=2,J=1,M=0) state with linearly polarized laser pulses at about 1.7 microm. These rotationally aligned J=1 molecules were then selectively photodissociated with a linearly polarized laser pulse at 220 nm after a time delay, and the velocity-dependent alignment of the (35)Cl((2)P(32)) photofragments was measured using 2+1 REMPI and time-of-flight mass spectrometry. The (35)Cl((2)P(32)) atoms are aligned by two mechanisms: (1) the time-dependent transfer of rotational polarization of the H(35)Cl(v=2,J=1,M=0) molecule to the (35)Cl((2)P(32)) nuclear spin [which is conserved during the photodissociation and thus contributes to the total (35)Cl((2)P(32)) photofragment atomic polarization] and (2) the alignment of the (35)Cl((2)P(32)) electronic polarization resulting from the photoexcitation and dissociation process. The total alignment of the (35)Cl((2)P(32)) photofragments from these two mechanisms was found to vary as a function of time delay between the excitation and the photolysis laser pulses, in agreement with theoretical predictions. We show that the alignment of the ground-state (35)Cl((2)P(32)) atoms, with respect to the photodissociation recoil direction, can be controlled optically. Potential applications include the study of alignment-dependent collision effects.     

Laser-induced UV photodissociation of 2-bromo-2-nitropropane: dynamics of OH and Br formation

Photoexcitation of 2-bromo-2-nitropropane (BNP) at 248 and 193 nm generates OH, Br, and NO(2) among other products. The OH fragment is detected by laser-induced fluorescence spectroscopy, and its translational and internal state distributions (vibration, rotation, spin-orbit, and Λ-doubling components) are probed. At both 248 and 193 nm, the OH fragment is produced translationally hot with the energy of 10.8 and 17.2 kcal∕mol, respectively. It is produced vibrationally cold (v" = 0) at 248 nm, and excited (v" = 1) at 193 nm with a vibrational temperature of 1870 ± 150 K. It is also generated with rotational excitation, rotational populations of OH(v" = 0) being characterized by a temperature of 550 ± 50 and 925 ± 100 K at 248 and 193 nm excitation of BNP, respectively. The spin-orbit components of OH(X(2)Π) are not in equilibrium on excitation at 193 nm, but the Λ-doublets are almost in equilibrium, implying no preference for its π lobe with respect to the plane of rotation. The NO(2) product is produced electronically excited, as detected by measuring UV-visible fluorescence, at 193 nm and mostly in the ground electronic state at 248 nm. The Br product is detected employing resonance-enhanced multiphoton ionization with time-of-flight mass spectrometer for better understanding of the dynamics of dissociation. The forward convolution analysis of the experimental data has provided translational energy distributions and anisotropy parameters for both Br((2)P(3∕2)) and Br?((2)P(1∕2)). The average translational energies for the Br and Br? channels are 5.0 ± 1.0 and 6.0 ± 1.5 kcal∕mol. No recoil anisotropies were observed for these products. Most plausible mechanisms of OH and Br formation are discussed based on both the experimental and the theoretical results. Results suggest that the electronically excited BNP molecules at 248 and 234 nm relax to the ground state, and subsequently dissociate to produce OH and Br through different channels. The mechanism of OH formation from BNP on excitation at 193 nm is also discussed.     

Formaldehyde photodissociation: dependence on total angular momentum and rotational alignment of the CO product

Quasiclassical trajectory calculations are reported to investigate the effects of rotational excitation of formaldehyde on the branching ratios of the fragmentation products, H2+CO and H+HCO. The results of tens of thousands of trajectories show that increased rotational excitation causes suppression of the radical channel and enhancement of the molecular channel. Decomposing the molecular channel into "direct" and "roaming" channels shows that increased rotation switches from suppressing to enhancing the roaming products across our chosen energy range. However, decomposition into these pathways is difficult because the difference between them does not appear to have a distinct boundary. A vector correlation investigation of the CO rotation shows different characteristics in the roaming versus direct channels and this difference is a potentially useful signature of the roaming mechanism, as first speculated by Kable and Houston in their experimental study of photodissociation of acetaldehyde [P. L. Houston and S. H. Kable, Proc. Nat. Acad. Sci. 103, 16079 (2006)].