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  • 1995-1999  (19)
  • 1990-1994  (24)
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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 106 (1997), S. 1346-1352 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Infrared diode laser absorption spectroscopy has been used to measure the CD3 radical photoproducts formed in the 193 and 222 nm photodissociation of dimethyl sulfoxide-d6. Quantum yields of CD3 have been determined to be 1.4±0.1 at 193 nm and 1.2±0.2 at 222 nm, compared to 2.0 for acetone-d6 at 193 nm. An analysis of transient waveforms reflecting the vibrational relaxation and radical recombination kinetics also yields an estimate of the nascent CD3 vibrational energy content by determining the fraction of total CD3 initially produced in the vibrationless state. The nascent CD3 population in the vibrational ground state decreases in order for the following photodissociation systems: CD3I at 248 nm, DMSO-d6 at 193 and 222 nm and acetone-d6 at 193 nm. The DMSO results are in good agreement with recent photofragment translational spectroscopy results and support a stepwise mechanism for the dissociation of DMSO at both wavelengths. © 1997 American Institute of Physics.
    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 109 (1998), S. 3431-3442 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A diode laser spectrometer incorporating a multi-pass Herriott type cell and frequency modulation detection was used to record a previously unaccessed region of the near-infrared singlet←singlet absorption spectrum of methylene between 10 000 cm−1 and 10 600 cm−1. With this spectrometer, signal-to-noise ratios close to the quantum noise limit have been attained. Identification of rovibronic transitions to five previously unobserved levels, K=1 a˜(0,9,0), K=2 b˜(0,1,0), K=2 a˜(1,6,0), K=3 b˜(0,1,0) and K=3 a˜(0,10,0), was made. Despite the fact that the present spectra access levels within approximately 1300 cm−1 of the barrier to linearity, the spectrum is dense and perturbed, characteristics in common with spectra recorded in many previous studies at shorter wavelengths. Recent spectroscopic observations of halomethylenes [J. Mol. Spectrosc. 188, 68 (1998)] had suggested that the CH2 spectrum might become simpler at longer wavelengths, but this was not evident in the observed spectra. The mixed nature of the singlet states is evidenced by the assignment of rovibronic transitions to levels containing primarily a˜ 1A1 state character. The new measurements provide a stringent test for modern theoretical models for CH2 and will enable refinement of the electronic potential surfaces. © 1998 American Institute of Physics.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 9213-9221 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Measurements of the ethyl radical -CH2 out-of-plane rocking vibrational fundamental by transient diode laser absorption spectroscopy are reported. The new data provide information on the structure of, and the barrier to internal rotation in, the radical, and how these quantities change on vibrational excitation. We find that the effective barrier decreases from approximately 17 cm−1 in the zero point level to 10 cm−1 in the excited vibrational level. The assigned data set now contains approximately 450 rotation-torsional transitions and has been fit to a model effective Hamiltonian. The derived molecular parameters generally reproduce the measured line positions to better than 0.01 cm−1, but this does not approach the estimated measurement accuracy of 0.001–0.002 cm−1. © 1999 American Institute of Physics.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 1717-1720 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report the use of time-resolved frequency modulation (FM) spectroscopy for the measurement of photochemically generated radicals. CN radicals from the 193 nm photodissociation of cyanogen (NCCN) have been detected using a phase-modulated cw Ti:sapphire ring laser, probing single rotational lines of the A 2Π←X 2Σ system. The combination of sensitivity with time and frequency resolution is more than adequate to record Doppler-broadened line shapes of collisionless photofragments. Significant signal-to-noise enhancement is demonstrated compared to a dual-beam transient absorption technique.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 9236-9245 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A Doppler-limited high resolution vibronic spectrum of the methylene (CH2) b˜ 1B1←a˜ 1A1 transition in the near-infrared wavelength region has been obtained using transient absorption techniques. The radical was produced by 308 nm excimer laser photolysis of ketene (CH2CO) in a flow system. The analysis of this spectrum confirms the reassignments of some previously observed bands as well as the presence of new vibronic bands predicted by a recent ab initio calculation [Green et al., J. Chem. Phys. 94, 118 (1991)]. We also measured the Doppler broadened profiles of low-J rotational lines of CH2 under collisionless conditions. From the line profile analysis, we find that the 308 nm photolysis of ketene produces fragments with isotropic and uncorrelated velocity and angular momentum distributions. The Doppler profiles also provide a view of the coincident product state distributions. The measured Doppler profiles are consistent with a rotational distribution of CO produced in coincidence with low energy CH2 states given by statistical phase space theory. The vibrationally excited coincident CO appears, however, to be produced about 2–3 times more efficiently than is predicted by various statistical theories. A frequency modulation (FM) technique has been adopted to improve the sensitivity of the transient absorption experiment. There is a significant improvement in the observed signal to noise ratio of the CH2 spectrum over the dual beam method previously used. © 1994 American Institute of Physics.
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  • 6
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Review of Scientific Instruments 70 (1999), S. 3259-3264 
    ISSN: 1089-7623
    Source: AIP Digital Archive
    Topics: Physics , Electrical Engineering, Measurement and Control Technology
    Notes: An apparatus has been constructed to study radical–radical reactions in the gas phase. It consists of a tubular quartz reactor in which radicals are produced by flash photolysis using an excimer laser as light source. The composition of the gas mixture is analyzed in situ by photoionizing sampled gases using the vacuum ultraviolet emission of a hollow cathode lamp and subsequent time-of-flight mass spectrometry. A simple arrangement of grids at the entrance to the flight tube is used to interrupt the constant flux of ions by application of a combination of constant and pulsed voltages. Individual mass spectra can be taken at a repetition rate of around 20 kHz following each photolysis event. Signal counts from a specified number of consecutive mass spectra are fed into a 2 GHz multiscaler and accumulated as a sampling-time-indexed series of mass spectra. This allows simultaneous observation of the concentrations of multiple transient or stable species on a millisecond time scale. To achieve a suitable signal-to-noise ratio, signals were typically accumulated over several tens of thousands of laser shots at a pulse rate of 10–15 Hz. © 1999 American Institute of Physics.
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  • 7
    ISSN: 1089-7623
    Source: AIP Digital Archive
    Topics: Physics , Electrical Engineering, Measurement and Control Technology
    Notes: An infrared time-resolved Fourier-transform emission spectrophotometer has been constructed and its use has been demonstrated. The instrument is based on a commercial interferometer combined with a CAMAC-based data acquisition system. The use of a transient digitizer permits acquisition of a single interferogram point at 100 time intervals following a single photoexcitation. The instrument operates in the "smooth scan'' mode. The combination of this mode of operation with the use of a transient digitizer provides great time efficiency for data acquisition because there is no mirror settling time at each optical retardation. Complete interferograms free from the artifacts associated with assembly of interferograms arising from multiple scans are available after each mirror scan. The maximum resolution of the present instrument is 0.1 cm−1, limited only by data storage considerations; the maximum resolution of the commercial interferometer is 0.02 cm−1 (with apodization) and could be utilized with long scans. The shortest time that can be resolved by the instrument, currently ∼1–2 μs, is limited only by the infrared detector/preamplifier combination. The longest time interval which is permitted between successive photochemical or photophysical events (nominally 3.16 ms) is limited by the slowest scan velocity of the moving mirror, (0.01 cm/s). Usable data can be acquired from 10 to 50 mirror scans, where acquisition, storage, and coaddition of a single 1 cm−1 resolution scan takes ∼5 min.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 6624-6631 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Far infrared laser magnetic resonance spectroscopy is used to measure components of 12 rotational transitions in the ground state of the HOCO radical. The transitions are all b-dipole in character in contrast to the a-dipole rotational spectrum previously reported [Radford, Wei, and Sears, J. Chem. Phys. 97, 3989 (1992)]. The new data determine the A rotational constant to high precision and allow the determination of several centrifugal distortion constants for the first time. The hyperfine coupling in the radical leads to observable splittings in several of the observed transitions and these are used to estimate two of the four expected nonzero hyperfine parameters in the radical.
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 3989-3995 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Part of the rotational spectrum of the hydroxyformyl radical, HOCO, and its deuterated analog has been detected at frequencies between 230 and 300 GHz. The radical was formed in a flow system by the reaction between chlorine atoms and formic acid. Analysis of the spectra yields reliable estimates of the rotational, centrifugal distortion and spin–rotational parameters describing the ground state of this species. The rotational constants derived for HOCO and DOCO are consistent with a planar equilibrium structure and are used to confirm that the carrier of the spectrum is the trans-geometrical isomer.
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 2337-2345 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The 248 and 193 nm photodissociation of the series of molecules RNCS and RSCN (R=H, CH3, C2H5) has been investigated. Laser-induced fluorescence of the radical NCS was used to probe the energy deposition in the R+NCS channel of this dissociation, however excitation to many vibrational states of NCS caused spectral congestion which prohibited direct measurement of populations of individual levels. A single-photon dissociation channel leading to RS and CN was observed for both isomers of all of the precursor molecules. While this was expected for the thiocyanate species, no direct channel to these products is available for the isothiocyanates. This observation is discussed in terms of an excited state isomerization of these molecules. Measured ratios of CN to NCS production for all compounds provide additional support for this mechanism and suggest a significant barrier to the process. Comparison of nascent laser-induced fluorescence (LIF) spectra of NCS with spectra obtained following different amounts of collisional relaxation suggests that all three vibrational modes were equally excited with a vibrational temperature of roughly 4500 K. The rotational temperature was estimated to be less than 1000 K. A spin–orbit population inversion was observed for all vibrational levels with approximately 75% of the population in the upper spin–orbit component of the vibrationless and low lying bending excited levels. No simple model is found to explain the photodissociation dynamics or the isomerization.
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