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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 4740-4748 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Time-domain experiments using femtosecond pulses have recently revealed the inertial aspect of the nuclear-orientation component of the optical Kerr effect in carbon disulfide. We present frequency-domain measurements, performed with the tunable-laser-induced grating technique, which also demonstrate the need to incorporate inertial behavior in models of the nuclear-orientation contribution to this ultrafast response. No previously suggested model, however, yields a fit to our data that passes standard goodness-of-fit tests at an acceptable level.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 4490-4493 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Angle-resolved photoelectron spectroscopy has been carried out on the valence shell of SiCl4 over the range of photon energies from 101.5 to 112.5 eV. Both intensities and angular distribution parameters β were monitored over the preionization resonances for silicon 2p. Little effect was seen for emission from the chlorine lone-pair orbitals 2t1 , 8t2 , and 2e, but striking effects were seen for the bonding 7t2 orbital. The resonant behavior was compared with photoabsorption data. The results are discussed in terms of direct participation of the resonantly excited electron and this process compared with spectator electron and shakeup processes.
    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 93 (1990), S. 3714-3715 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Resonance-enhanced multiphoton ionization (2+1 REMPI) spectroscopy near 243 nm was used to detect H and D photofragments of the 193 nm photolysis of C2HD. Measurements were performed in a molecular beam, laser photolysis apparatus, equipped with a time-of-flight mass spectrometer. The measured H/D ratio of 2.85±0.3 may indicate nonadiabatic surface hopping occurs between 2 3 A' and 1 3 A' and/or 2 1 A'and 1 1 A'surfaces in exit channels leading to ground state C2H(X˜ 2 Σ+ )+H(2 S) fragments in the predissociation of C2H2.
    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 83 (1985), S. 2284-2292 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The Ar++CO→CO+(v=0–6)+Ar charge transfer reaction is studied at thermal energy in a flowing afterglow and the vibrational state distribution is determined by laser-induced fluorescence on the CO+(A 2Π–X2Σ+) bands. The nascent vibrational state distribution is (0.06±0.04)v=0 @B:(0.07±0.02)v=1 @B:(0.09±0.02)v=2 @B:(0.15±0.03)v=3 @B:(0.21±0.03)v=4@B: (0.27±0.02)v=5 @B:(0.15±0.02)v=6. The rate constant for CO+(v=4) deactivation by CO is measured to be 6.0±2.5×10−10 cm3 s−1; the similarity of this rate constant to that for CO+(v=1) deactivation by CO (5.0±2.0×10−10 cm3 s−1) suggests that vibrational deactivation proceeds by a charge transfer mechanism. The Ar++CO reaction is described as proceeding via a bent ArCO+ intermediate that forms in a side-on attack. Vibrational excitation may then result from delocalization of the bonding electron density of CO and the corresponding dynamical changes in the CO bond length in the intermediate.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 83 (1985), S. 601-610 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The nascent vibrational state distribution of the N++CO→CO+(v=0–2)+N charge transfer reaction is measured at thermal energy. The reaction is carried out in a flowing afterglow and the vibrational state populations are determined by laser-induced fluorescence on the CO+(A 2Π−X 2Σ+) system. The nascent vibrational state distribution for the N++ CO reaction is (0.71±0.05)v=0:(0.27±0.04)v=1:(0.02±0.01)v=2. The observed vibrational distribution suggests that neither a long-range Franck–Condon mechanism nor an energy resonant process adequately describes the charge transfer reaction. A dual channel mechanism of the reaction is considered, in which a fraction of the reactive collisions proceed by a long-range Franck–Condon mechanism while the remainder proceed via a long-lived NCO+ intermediate. The intermediate may lead to the observed extent of CO+ vibrational excitation either through statistical partitioning of the energy or by dynamical changes in the CO bond length through specific molecular orbital occupancies.
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 5138-5140 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The energies of six stationary points on the OH+CO→HOCO→H+CO2 potential energy surface have been calculated using the G3 and CBS-QB3 methods. An analysis combining ab initio and experimental enthalpies yielded ΔHf298 K (trans-HOCO)=−42.9±1.5 kcal mol−1 (−43.8±1.4 kcal mol−1) at the G3(CBS-QB3) level of theory. These results confirm the revised HOCO heat of formation derived from photoionization spectroscopy and suggest that the HOCO potential well is 8.8 kcal mol−1 shallower than previously thought. We discuss the implications of these results for accurate Rice–Ramsperger–Kassel–Marcus modeling or quantum mechanical scattering calculations of the OH+CO reaction. © 2000 American Institute of Physics.
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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. 6459-6470 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Pure rotational spectra of the IO radical have been observed for vibrational levels up to v=13 in the X1 2Π3/2 state and up to v=9 in the X2 2Π1/2 state. Isotopically enriched I18O rotational spectra have been observed for vibrational levels up to v=5 in both the X1 and X2 states. These are the first high-resolution spectra of any kind reported for the X2 state and greatly extend the available data for the X1 state. The data for both isotopomers have been fitted simultaneously to a single set of 2Π parameters with fixed isotopic ratios. The isotope relations among the parameters have provided a means of decorrelating the electron spin-rotation constant γ from the fine-structure centrifugal distortion constant, AD, and have allowed the first determination of an effective value for γ. The rotation–vibration constants correspond to the equilibrium molecular properties re(X1)=186.762 pm, re(X2)=188.468 pm, ωe(X1)=681.69 cm−1, and ωe(X2)=645.29 cm−1. These constants have been used to calculate X1 and X2 Rydberg–Klein–Rees potentials encompassing energies up to 40% of the dissociation limit. A complete set of hyperfine coupling constants has been determined for the first time and interpreted using appropriate relativistic atomic radial integrals. © 2001 American Institute of Physics.
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  • 8
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Review of Scientific Instruments 56 (1985), S. 2161-2163 
    ISSN: 1089-7623
    Source: AIP Digital Archive
    Topics: Physics , Electrical Engineering, Measurement and Control Technology
    Notes: A variable temperature cryogenic photoacoustic detector has been developed for making spectroscopic measurements on gas phase molecules. Temperatures in the range of 77–300 K are obtained with this device.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Review of Scientific Instruments 58 (1987), S. 60-68 
    ISSN: 1089-7623
    Source: AIP Digital Archive
    Topics: Physics , Electrical Engineering, Measurement and Control Technology
    Notes: A new approach to the design of a fiber-optic interface that links a commercial sampling head to its matching time-domain reflectometer (TDR)/sampler oscilloscope plug-in unit is reported. Three fiber-optic links replace the wired signal paths of the original design that convey the vertical error signal, the feedback signal, and the horizontal sampling command signal between the sampling head and the oscilloscope sampling plug-in. The dielectric fiber pigtails allow the use of the sampling head inside objects that need to be electromagnetically insulated from the instrumentation system. Low-frequency analog links are used to convey the error and feedback signals. The sampling command signal is conveyed via a link where a powerful, fast-rise infrared laser pulse is generated. The laser pulse is used to trigger an avalanche transistor in the strobe generator circuit of the sampling head by directly coupling the optical energy to the transistor chip. This direct method of detection minimizes the time jitter introduced to the strobe signal, resulting in a bandwidth of 4 GHz. Some of the results of the tests which were carried out on the system are reported.
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 107 (1997), S. 2300-2307 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The highly structured visible absorption spectrum of the bromine dioxide radical, OBrO, has been observed in the 15 500–26 000 cm−1 region. The spectrum is dominated by a long progression in the Br–O symmetric stretching motion (ν1′) and a series of short progressions built on the bending mode (ν2′); there are no features associated with the excitation of the antisymmetric stretching mode (ν3′). The spectrum also contains numerous transitions originating from the (0,1,0) and (1,0,0) vibrational levels of the electronic ground state, X(2B1). A simultaneous fit to all of the observed vibronic features yielded the frequencies ν1″=799.4 cm−1, ν2″=317.5 cm−1, ω1′=641.5 cm−1, ω2′=210.7 cm−1, and a band origin T0=15 863 cm−1. Franck–Condon simulations combined with ab initio calculations of the four lowest OBrO doublet electronic states identify the spectrum as arising from the C(2A2)←X(2B1) electronic transition. © 1997 American Institute of Physics.
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