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  • 1
    Digitale Medien
    Digitale Medien
    Photodissociation of acetylene at 193.3 nm (1985)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 89 (1985), S. 4744-4751 
    Details
    Quelle: ACS Legacy Archives
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1021/j100268a019
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  • 2
    Digitale Medien
    Digitale Medien
    Axis-switching transitions and the stimulated emission pumping spectrum of HCN (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 2284-2298 
    Details
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Six of the 14 unidentified bands in the stimulated emission pumping (SEP) spectrum of HCN are shown to be forbidden transitions to l‘=1 e parity levels of the ground state. The band origins agree with predictions within the error of the anharmonic expansion; the rotational constants, when corrected for rotational-l doubling, agree within experimental error. Rotational-l resonance between l‘=0 and l‘=2 is found in highly excited bending levels, confirming the extrapolation of the rotational-l resonance and doubling constant q2 from microwave and infrared measurements to 17 000 cm−1. The rotational intensity of the l‘=1 bands due to the axis-switching mechanism of Hougen and Watson [Can. J. Phys. 43, 298 (1965)] is shown to be greater than some of the observed allowed rotational transitions to l‘=2 when laser polarization effects are taken into account. A qualitative Franck–Condon analysis of the SEP spectrum provides unusually strong evidence for the axis-switching mechanism. The eight remaining unassigned bands are evidently perturbed and are assigned based on agreement between sums of observed rotational constants and sums of zero-order (unperturbed) rotational constants predicted by the anharmonic expansion, the magnitude of the rotational-l resonance, and the expected Franck–Condon factors.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1063/1.463120
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  • 3
    Digitale Medien
    Digitale Medien
    Vibrational energy transfer of very highly vibrationally excited NO (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 5111-5122 
    Details
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The dependence of vibrational energy transfer on vibrational excitation has been studied using the stimulated emission pumping technique to efficiently prepare a large range of specific vibrational states of the nitric oxide molecule in its ground electronic state. Laser induced fluorescence was used to detect collisionally relaxed NO. The self-relaxation rate constants of NO(v(very-much-greater-than)1) were up to 200 times larger than that of NO(v=1). Multiquantum relaxation was found to be important at high energy and was quantified at 3.8 eV. Self-relaxation rate constants of 15N18O as well as 14N16O were measured and a large isotope effect was observed. Relaxation of NO(v‘=22) with H2 was also investigated. Theoretical explanations of our experimental results were attempted and it is shown that at vibrational energy up to ≈3 eV the qualitative trends observed in these experiments such as the mass effect and the multiquantum relaxation can be explained by Schwartz–Slawsky–Herzfeld theory. A simple explanation of the anomalously high NO self-relaxation rate is given. The large acceleration of the vibrational relaxation rate above 3.0 eV is coincident with the energetic onset of high energy (NO)2 isomer complexes. More theoretical and experimental work is needed to explain the quantitative aspects of these observations.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1063/1.462753
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  • 4
    Digitale Medien
    Digitale Medien
    State-to-state spin–orbit and rotational energy transfer of very highly vibrationally excited nitric oxide (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 5123-5128 
    Details
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: PUMP–DUMP–PROBE experiments were performed on nitric oxide (NO) in order to study the rotational and spin–orbit energy transfer in a highly vibrationally excited diatomic. Total depopulation as well as state-to-state rotational and spin–orbit energy transfer rate constants were measured for v=8 and 19 of the ground electronic state. By comparing this new set of results with previously measured results for v=2 [Aa. Sudbo and M. M. T. Loy, J. Chem. Phys. 76, 3646 (1982)] the vibrational influence on the rotational and spin–orbit energy transfer dynamics could be evaluated. Total depopulation rate constants for individual rovibrational states were found to be very similar for v=2, 8, and 19. State-to-state rotational energy transfer rate constants could be compared for v=8 and 19, and again only small differences were found. It appears that vibrational energy does not have a significant impact on the rotational and spin–orbit energy transfer dynamics for NO–NO collisions.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1063/1.462754
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  • 5
    Digitale Medien
    Digitale Medien
    State-selective detection of CO using a tunable ArF excimer laser (1988)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 2588-2589 
    Details
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: CO molecules in their electronic and vibrational ground state were state selectively detected using a tunable ArF excimer laser. Rotational state selectivity is due to the one-photon resonance of the spin-forbidden a 3Π, v'=2←X 1∑+,v‘=0 transition. Subsequent absorption of two additional ArF laser photons yields, via a dissociative continuum, electronically excited C(3 1P) atoms, whose fluorescence is detected.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1063/1.455055
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  • 6
    Digitale Medien
    Digitale Medien
    State-specific neutral time-of-flight of CO from ketene photodissociation at 351 nm: The internal energy distribution of CH2(X˜ 3B1) (1996)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 105 (1996), S. 4550-4555 
    Details
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Metastable time-of-flight (TOF) spectroscopy was used to measure the translational energy distribution of specific rotational states of CO formed from ketene photodissociation (CH2CO→CH2+CO) at 351 nm. This distribution could be directly related to the internal energy distribution of the other fragment (X˜ 3B1 CH2) formed in the reaction, thereby giving a correlated distribution of the internal states of the fragments. This technique overcomes the spectral complexity associated with detection the X˜ 3B1 state CH2. Previous measurements of the CO rotational distribution were simulated theoretically using the impulsive model and zero-point vibrational energy considerations. These models predicted that the rotational distributions of CO and CH2 should be uncorrelated, that ∼10% of the CH2 should be vibrationally excited with one quantum in the bending mode, and that the rotational energy distribution of CH2 should peak near zero. Measurements presented in this paper show a slight anticorrelation of CO and CH2 rotations, no vibrational excitation of CH2 and Gaussian-like rotational energy distributions of CH2 that peak at ∼1 kcal/mole and have a full width at half-maximum of ∼0.8 kcal/mol. Qualitative explanations for this behavior are presented. © 1996 American Institute of Physics.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1063/1.472538
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  • 7
    Digitale Medien
    Digitale Medien
    Reactive O2(v≥26) as a source of stratospheric O3 (1996)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 775-776 
    Details
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The reaction of vibrationally excited O2 (v≥26) with ground-state O2 has been proposed as a source of stratospheric O3. The O2 (v≥26) yield from O3 photolysis has now been determined at 193 and 226 nm. Here we examine the wavelength dependence of the new mechanism. We find that the new O3 production is most sensitive to the O2 (v≥26) yield near 220 nm. Shorter and longer wavelengths are less important for this new production mechanism. © 1996 American Institute of Physics.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1063/1.471642
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  • 8
    Digitale Medien
    Digitale Medien
    The correlated product state distribution of ketene photodissociation at 308 nm (1996)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 7460-7474 
    Details
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The correlated product state distribution for ketene photodissociation (CH2CO→CH2+CO) at 308 nm has been measured by using quantum-state-specific metastable time-of-flight (TOF) spectroscopy. This distribution is a matrix whose elements are the probability that if CO is produced in the dissociation with quantum-state ||nCO〉, CH2 will be produced with quantum-state ||nCH2〉. It was found that ketene photodissociation yields CH2 in three resolved states; the 1A1(000), and 1A1(010) states of CH2 are the major channels, while the 3B1 state is a minor channel. In addition to this scalar distribution, the vector correlations between the recoil velocity and the angular momentum of the CO fragment (v⋅j correlation), expressed by the β00(22) bipolar moment, have also been obtained as a function of the kinetic energy release of the photoreaction. The correlated product state distribution was found not to follow the predictions of phase space theory, suggesting that dynamic hindrances exist in the photoreaction that have not been previously observed. A phase space theory calculation with restricted impact parameter values was also performed and compared to experiment. The impact parameter restricted phase space theory more accurately reproduced all of the correlated product state information obtained in this work as well as previous uncorrelated product state distributions for CH2 and CO. Both the ranges and the values of the allowed impact parameters obtained from these restricted calculations increase as the rotational energy of CO increases. Also, the values of the allowed impact parameters for 1A1(010) CH2 are larger than for 1A1(000) CH2. This strongly suggests that C–C–O bending modes are hindered at the transition state and therefore play an important role in the photodissociation. © 1996 American Institute of Physics.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1063/1.471459
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  • 9
    Digitale Medien
    Digitale Medien
    Infrared multiphoton dissociation of ethyl and methyl acetate (1988)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 92 (1988), S. 5379-5387 
    Details
    Quelle: ACS Legacy Archives
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1021/j100330a013
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  • 10
    Digitale Medien
    Digitale Medien
    Production and photodissociation of trichloromethyl radicals in a molecular beam (1991)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 95 (1991), S. 2799-2802 
    Details
    Quelle: ACS Legacy Archives
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1021/j100160a031
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