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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of the American Chemical Society 114 (1992), S. 6926-6928 
    ISSN: 1520-5126
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Analytical chemistry 56 (1984), S. 457-462 
    ISSN: 1520-6882
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 3477-3482 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Tert-butyl bromide is photodissociated at 277.3 nm (in the tail of the first absorption continuum). Both fragments, i.e., the t-butyl radical and the Br(2P1/2) atom, are detected by laser MPI-TOF mass spectrometry. Seeded, supersonic beams of this pseudosymmetric top molecule are readily focusable and orientable (via its first-order Stark effect) using the electrostatic hexapole lens. The linearly polarized laser-induced photofragmentation technique reveals unusually high degrees of orientation, significantly greater than that for t-C4H9I, due to the less serious hyperfine disorientation effect for the Br- (vs I-) containing molecule. Thus t-C4H9Br is an excellent candidate reagent for reactive asymmetry scattering studies of the steric effect via the oriented molecule beam method.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 2099-2106 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The tert-butyl iodide molecule is readily focused with the electrostatic hexapole, via its first-order Stark effect as a pseudo-symmetric top. The pulsed, seeded supersonic focused beam, characterized by 〈cos θ〉=Vth/ V0 (where θ is the angle between the molecular dipole axis μ and the electric field E; ±V0 the hexapole "rod voltage,'' and Vth the so-called threshold voltage), passes into a small homogeneous electric field in which it is oriented. The degree of laboratory orientation achieved is measured using the method of linearly polarized laser-induced photofragmentation [S. R. Gandhi, T. J. Curtiss, and R. B. Bernstein, Phys. Rev. Lett. 59, 2951 (1987)], operating (at three laser wavelengths) on the I(2P3/2) and I(2P1/2) as well as the t-C4H9 radical photofragments. The results show that the oriented beam molecules of t-butyl iodide (at a rotational temperature near 15 K) have a higher degree of orientation than the prototype CH3I molecules (JKM state-selected and focused similarly), explainable by the greater importance of the so-called hyperfine disorientation effect for the prolate symmetric top (CH3I) than for the t-C4H9I. For the latter, orientations with photofragment up–down asymmetry ratios as large as a factor of 10 can be achieved, suggesting that t-C4H9I is an excellent candidate reagent for reactive asymmetry studies.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 116 (2002), S. 4490-4496 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photodissociation dynamics of acetyl bromide was investigated at 234 nm. A two-dimensional photofragment ion-imaging technique coupled with a [2+1] resonance-enhanced multiphoton ionization scheme was utilized to obtain speed and angular distributions of the nascent Br(2P3/2) and Br*(2P1/2) atoms. The recoil anisotropies for the Br and Br* channels were measured to be β=1.47±0.05 for Br and 1.44±0.05 for Br*. The relative quantum yield for Br* was found to be ΦBr*=0.37±0.05. The probability of nonadiabatic transition between two A′ states was determined to be 0.36. Broad Gaussian distributions were observed for the total translational energy distributions corresponding to the Br and Br* channels. The soft radical limit of the impulsive model adequately modeled the related energy partitioning. It is proposed that the σ*←n transition localized on the C–Br chromophore mainly contributes to the initial transition of acetyl bromide at 234 nm. © 2002 American Institute of Physics.
    Type of Medium: Electronic Resource
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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. 9739-9746 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photodissociation of Br2 at 234 and 265 nm was investigated using a velocity map imaging technique via one- and two-photon excitation. The speed and angular distributions of the bromine ions obtained via one-photon excitation following state selective ionization reveal a unique transition to the 1441 3Σu+(1u) state. This state dissociates further into Br(4p 2P3/2)+Br(4p 2P1/2) at 234 nm, and into Br(4p 2P3/2)+Br(4p 2P1/2) and Br(4p 2P3/2)+Br(4p 2P3/2) at 265 nm, with relative quantum yields of Φ(Br(4p 2P3/2)+Br(4p 2P1/2))=0.96 and Φ(Br(4p 2P3/2)+Br(4p 2P3/2))=0.04. The proportionality constant k, related to the relative [2+1] REMPI strengths of atomic bromine (Br 2P1/2/Br 2P3/2) was determined to be 0.42±0.02 for Br(4p 2P1/2) detected at 234.0 nm and for Br(4p 2P3/2) at 233.7 nm, and 0.73±0.02 for Br 2P1/2/Br 2P3/2 at 264.9 nm to detect Br(4p 2P1/2) and 264.8 nm to detect Br(4p 2P3/2). Image analysis of the ions and photoelectrons obtained by two-photon excitation at various wavelengths in the range of 229.4–237.6 nm shows that some fragmented bromine atoms are in highly excited Br(5s 4PJ:J=5/2, 3/2, 1/2) states, and that there exists superexcited Rydberg states converging to the asymptotes, Br(4p 2P)+Br(5s 4P) near the ionization threshold. © 2001 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 115 (2001), S. 10745-10752 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photodissociation dynamics of CF3Br in the A-band has been investigated utilizing a two-dimensional photofragment ion-imaging technique coupled with a state-selective resonance-enhanced multiphoton ionization scheme. The total translational energy distributions for the Br(2P3/2) and Br*(2P1/2) channels are well characterized by Gaussian functions with average translational energies of 183 and 151 kJ/mol, respectively. The recoil anisotropies were measured to be β=0.66 for Br and 1.83 for Br*. It was found that Br* production is preferred, with a relative quantum yield of 0.80. The reduction in the recoil anisotropy for Br results from nonadiabatic coupling between the 1Q1 and 3Q0 states. The fraction of molecules that dissociate via a distorted pathway induced by symmetry reduction from C3v to Cs is estimated to be 0.11. © 2001 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 1427-1432 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photodissociation dynamics of t-BuOOH at 213 nm has been studied using degenerate four-wave mixing spectroscopy. The internal energy distribution, Λ-doublet ratio and spin-orbit state ratio of OH (X2Π, v″=0) fragments were extracted. The OH radicals were found to be vibrationally cold with an average rotational energy of 1726 cm−1, indicating that 5.0% of the available energy was transferred into the OH rotational degree of freedom. A Gaussian distribution of product rotational energy was observed. The population was found to be distributed statistically between the two spin-orbit states. A preferential population of the π+ Λ-doublet was observed irrespective of N without inversion. The observed Λ-doublet nonequilibrium implies that splitting of energy levels may occur because of the breaking of symmetry due to substitution. We suggest that the hydroxyl part should be the dominant chromophore for the absorption of t-BuOOH at 213 nm. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 114 (2001), S. 10368-10374 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photodissociation dynamics of allyl bromide and chloride have been investigated at 234 nm using a two-dimensional photofragment ion imaging technique coupled with a [2+1] resonance-enhanced multiphoton ionization scheme. After absorbing a photon, allyl bromide dissociates into C3H5+Br(2Pj;j=1/2,3/2) exclusively via the repulsive surfaces. The enhanced contribution of the singlet state to the initial transition is attributed to intensity borrowing from the nearby 1(π,π*) state. Trimodal translational energy distributions of Cl(2Pj;j=1/2,3/2) have been observed after the photolysis of allyl chloride. Low-velocity components with Boltzmann shapes are produced via internal conversion between the initially pumped 1(π,π*) state and the vibrationally excited ground state. Middle-velocity components with Gaussian shapes originated from curve crossing between the bound 1(π,π*) state and the dissociative 1(π,σ*) state. High-velocity components are produced via curve crossing from the 1(π,π*) state to the 1(n,σ*) state. The enhanced curve crossings in exit channels are attributed to the non-planar geometry of the parent molecule and torsional torque induced by the initial 1(π,π*) transition. The location of the curve crossing between the 1(π,π*) state and the 1(n,σ*) state has been estimated to be (approximate)40 000 cm−1 based on the localized available energy. © 2001 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 4005-4012 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photodissociation dynamics of CBrCl3 was studied near 234 and 265 nm using a two-dimensional photofragment ion imaging technique. Bromine fragments monitored in this study were produced via direct dissociation of CBrCl3, represented by CBrCl3→CCl3+Br(2P1/2)/Br(2P3/2). The branching ratio of Br(2P1/2) (denoted Br*)/Br(2P3/2) (denoted Br) showed strong excitation energy dependence. The product quantum yields at two different excitation wavelengths were Φ 234 nm(Br*)=0.31±0.01 and Φ 265 nm(Br*)=0.68±0.02, respectively. The speed and angular distributions of Br* and Br fragments were determined. Similar values of β(234 nm)=−0.44 and β(265 nm)=−0.47 for Br were observed, while β values for Br* were found to be markedly different, β(234 nm)=−0.34 and β(265 nm)=1.43. The strong curve crossing, 1Q1→3Q0, and the angular distribution of Br* suggesting a typical perpendicular transition, were observed at 234 nm photodissociation.© 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
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