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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 7490-7499 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The OH product state distribution from the reaction O(1D)+H2(v)→OH(v‘,J‘,Ω,Λ)+H was determined by laser-induced fluorescence (LIF) in the Δv=−3 band for v‘=3 and 4 with resolution of the J‘, Ω, and Λ sublevels. The rotational state population distribution is inverted strongly in v‘=3, weaker in v‘=4. There is a higher propensity for production of OH in the Π(A') Λ-sublevels. Vibrationally excited H2 was used for a part of the experiments. Excitation was achieved by stimulated Raman pumping (SRP). The population ratio of the vibrational states was determined to be P(v=3)/P(v=4)=3.5 for the reaction with H2(v=0) and 3.0 when there is H2(v=1) in the reaction chamber. Higher OH product states are populated than it would be expected from the mean available energy of the reaction. The translational energy of the reactants is transferred into OH rotation.
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  • 2
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Hydrogen peroxide has been optically excited at a wavelength of 266 nm and the OH photofragment completely characterized by Doppler and polarization spectroscopy using the laser-induced fluorescence technique. The entire internal state distribution (vibration, rotation, spin, and Λ components), translational energy, angular distribution, rotational alignment, and vector correlations between rotational and translation motions of OH products is measured. The hydroxyl radicals are formed in the X 2Π3/2,1/2 ground state with 90% of the available energy (248 kJ/mol) being released as OH recoil translation. The angular distribution is nearly a sin2 θ distribution about the electric vector of the photolysis laser. The internal motion of OH is vibrationally cold (no vibrationally excited OH was found) while the rotational excitation in v‘=0 can be described by a Boltzmann distribution with a temperature parameter of Trot=(1530±150) K. The two spin states are found to be populated nearly statistically, in contrast to the Λ components which show an increasing inversion with increasing OH rotation. The observed profiles of recoil Doppler broadened spectral lines are strongly dependent on the nature of the transition, the excitation–detection geometry, and the relative polarizations of the dissociating and analyzing laser light. However, the line intensities show only a minor dependence on geometry and polarization indicating a low alignment of OH photofragments (A(2)0≤0.1). For the first time the vector correlation between product rotational and translational motions was analyzed and evaluated in terms of the three bipolar moments β20(20), β00(22), and β20 (22). The bipolar moment β20(20) corresponds to the conventionally defined anisotropy parameter β=2β20(20) =−0.71. The angular distribution peaks in the direction perpendicular to the electric vector of the dissociating laser light, indicating the predominant electronic excited state in H2O2 being of 1A symmetry. The moment β00(22) increaseswith JOH showing a bias towards vOH and JOH being parallel to one another. The moment β20(22) is a measure of the mutual correlation of the fragment translational and rotational vectors and the transition dipole vector μ in the parent molecule. The positive value of this moment [β20(22)=0.11] indicates that the expectation value of 〈J2y〉 should be very small when μ is parallel to the z axis and vOH perpendicular to μ (x axis). 〈J2x〉 originates in the torsional motion in the H2O2 parent molecule, while 〈J2z〉 reflects the bending vibration of nearly planar H2O2 where the H atoms are in the trans position.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 85 (1986), S. 40-44 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photofragmentation of hydrogen peroxide has been investigated at an excitation wavelength of 266 nm using polarized laser beams. Doppler spectroscopy in connection with the laser induced fluorescence technique was applied to determine the nascent translational distribution of OH products. The hydroxyl radicals are formed in their electronic ground state, X 2Π3/2,1/2. The released energy is transformed almost exclusively in translation of these photoproducts. The Q1(4) transition in OH(X 2Π3/2→A 2Σ+) was used to study the anisotropic angular distribution of recoiling OH photofragments and analyzed to obtain information about the lifetime and symmetry of the excited dissociative state. The Doppler profiles for different directions of the electric field vectors of dissociation and probe laser relative to the detector axis have been determined for two different geometries. The angular distribution measured by Doppler spectroscopy, peaks in the direction perpendicular to the electric vector of the dissociating laser light, indicating that the predominant electronic excited state in H2O2 must be of 1A symmetry. An upper limit for the lifetime τ of the excited H2O2 parent molecule before dissociation is τ≤6×10−14 s.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 117 (2002), S. 2141-2150 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The state-resolved and isotope-specific detection of nascent ClO generated from the photodissociation of Cl2O parent molecules is performed by observing single-color (2+1) resonance enhanced multiphoton ionization (REMPI) spectra following excitation in the wavelength range from 336 to 344 nm; additionally state-resolved detection of nascent ClO is performed by observing single-color two photon laser-induced fluorescence. The REMPI spectrum is assigned to the ClO(C 2Σ−,v′=0←X 2ΠΩ,v=0) transition. The population of rotational states up to J=130 is evidence of large rotational excitation induced by a strong dependence of the excited potential energy surface (PES) on the Jacobi angle γ. Formation of the 2Π3/2 spin-orbit state is preferred: P(2Π1/2):P(2Π3/2)=0.30±0.05 suggesting significant radiationless transfer from the excited PES to closely lying neighboring states. The anisotropy parameter for the transition is determined to be β=0.35 independent of the ClO quantum state. The principal excited electronic state is assigned to a 1B2←1A1 transition, in agreement with recent ab initio calculations. The measured β value is smaller than the limiting value of 1.0, suggesting dynamic reasons and simultaneous excitation to more than one PES. A fast and direct fragmentation process is deduced, where the upper limit for the lifetime of the excited dissociative state is calculated to be 300 fs. © 2002 American Institute of Physics.
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  • 5
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photodissociation dynamics of COCl2 has been studied by monitoring ground Cl(2P3/2) and spin–orbit excited Cl*(2P1/2) fragments by applying a novel technique where the three-dimensional momentum vector of a single reaction product is directly determined. The photodissociation at 235 nm produces exclusively three fragments: COCl2+hν→CO+2Cl. The kinetic energy distributions of Cl and Cl* are bimodal and exhibit a different behavior for the different spin–orbit states. Our attention was turned to the dependence of the anisotropy parameter β on the fragment velocity which was observed for the first time. For both spin–orbit states the anisotropy parameter differs clearly for slow and fast chlorine atoms, where a pronounced change from the value ∼0.7 to zero at about 20 kJ/mol is observed. Slow chlorine atoms are released isotropically and predominantly in the ground state Cl whereas fast chlorine atoms have an anisotropy parameter close to the theoretically limiting value and are distributed between ground and excited state Cl. These observations can be explained by a sequential decay where the first Cl fragment is released in a fast process characterized by the nonvanishing positive β parameter and a lifetime of ≤210 fs, whereas the second Cl fragment is released after a period which is long on a rotational time scale. A significant contribution of a symmetric mechanism can be excluded. © 2002 American Institute of Physics.
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 115 (2001), S. 6418-6425 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The ∼235 nm photodissociation of CH3CFCl2 pre-excited to three, four, and five quanta of C–H methyl stretches was studied to investigate the effect of internal parent excitation on the dynamics of two- and three-body photofragmentation. The ∼235 nm photons also tagged spin-orbit ground Cl 2P3/2 [Cl] and excited Cl 2P1/2 [Cl*] state photofragments, via (2+1) resonantly enhanced multiphoton ionization in a time-of-flight mass spectrometer. Monitoring the shapes of 35Cl and 35Cl* time-of-arrival profiles revealed their energies and angular distributions and showed broad and unstructured fragment kinetic energy distributions. Although a significant amount (∼50%) of the available energy is transferred into internal energy of the CH3CFCl fragment, the spatial Cl distribution is characterized by a nonvanishing anisotropy parameter, β, which indicates at a fast dissociation of the parent molecule along the C–Cl dissociation coordinate. Moreover, β for Cl changes from a slightly positive value to a negative value, while that for Cl* increases when the pre-excitation is increased from three to five quanta of C–H methyl stretches. This is attributed to the promotion of one of the nonbonding electrons located on the Cl atoms to the σ* antibonding C–Cl orbital and involvement of several upper states with different symmetry properties. © 2001 American Institute of Physics.
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  • 7
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 6210-6226 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: State-to-state rotational energy transfer of ground state NH(X 3Σ,v=0,J,N) in collisions with Ne is examined. NH is exclusively generated in the metastable NH(a 1Δ) state via photodissociation of hydrazoic acid at a wavelength of 266 nm. The strongly forbidden NH(a 1Δ→X 3Σ−) intercombination transition around 794 nm is used to generate single state NH(X 3Σ−,v=0,J,N) applying the stimulated emission pumping technique. The ground state radicals are detected after a certain delay time with laser induced fluorescence (LIF) using the intense NH(A 3Π←X 3Σ−) transition around 336 nm with respect to all quantum states. The collision induced energy flux between the different rotation and spin levels is studied in detail and a comprehensive set of state-to-state rate constants for inelastic collisions of NH(X 3Σ−,v=0,J,N) with Ne up to N=7 which include the effect of multiple collisions is given. The state-to-state rate constants are obtained by the use of an iterative integrated profiles method. We find a propensity for (ΔN=0, Δi=±1) and (ΔN=±1, Δi=0) transitions where N represents the quantum state for nuclear rotation and i represents the index of the spin component Fi. In most cases the energy transfer which changes the spin component and conserves the nuclear rotation quantum number N (ΔN=0, Δi=±1), is the most effective energy transfer in collisions with Ne. The energy dependence of the transition efficiency concerning only the nuclear rotation quantum number N obeys an energy-gap law (EGL). © 2000 American Institute of Physics.
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 9465-9468 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new method is presented to examine state-to-state rotational energy transfer in ground state NH(X 3Σ−,v=0,J,N). NH(X 3Σ−) is generated via state selective stimulated emission pumping using the strongly forbidden NH(a 1Δ→X 3Σ−) intercombination transition around 794 nm after foregoing photodissociation of HN3 at a wavelength of 266 nm. Products are detected by laser induced fluorescence (LIF). Chemically relevant collision dynamics including spatial processes can be studied for the first time in v=0 of the electronic ground state. State-to-state rate constants for inelastic collisions of NH(X 3Σ−,v=0,J=3,N=3) with Ne are presented. © 1999 American Institute of Physics.
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 4481-4489 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Vibrational overtone excitation of HCN in the wavelength region 6 500 cm−1–18 000 cm−1 is used to initiate the endothermic reaction of chlorine and hydrogen atoms with HCN. HCN is excited to the overtone levels (002), (004), (302), (105), and (1115). The labeling of the vibrational levels (ν1ν2l2ν3) corresponds to the normal modes ν1=CN, ν2=bend, ν3=CH, and l2=vibrational angular momentum. The product state distribution of CN(X 2Σ+) is completely analyzed by laser induced fluorescence (LIF). Excitation of the first overtone of CH-stretch leads to vibrationally excited CN in the reaction of Cl+HCN(002), implying the existence of a long living complex. The CN vibrational excitation increases with increasing H–CN stretch excitation. However, a slightly higher CN vibrational excitation is found when at the same internal energy of HCN three quanta of CN-stretch and two quanta of CH-stretch are excited. Therefore, the energy is not completely redistributed in the collision complex. The ratio of rate constants between the reactions of HCN(004) and HCN(302) with Cl is 2.8±0.6. The CN product vibrational excitation decreases again, when HCN is excited to the (105) state. At these high HCN vibrational energies the reaction mechanism seems to change toward a more direct reaction where the time left is not sufficient for energy randomization. The reaction of hydrogen with HCN(004) leads to CN-products with a similar vibrational distribution, as in the case of chlorine, but with a lower rotational excitation. The reaction H+HCN(302) shows no significant generation of CN products and a lower limit of the ratio of rate constants, k(004)/k(302)(approximately-greater-than)4, is obtained. © 1996 American Institute of Physics.
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