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  • 1
    Electronic Resource
    Electronic Resource
    Rotational, fine, and hyperfine structure in the high-resolution electronic spectrum of ArOH and ArOD (1991)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 7086-7098 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A number of vibrational bands of the A˜ 2Σ+↔X˜ 2Π electronic spectrum of both ArOH and ArOD have been investigated by laser induced fluorescence with a high-resolution, pulsed laser system yielding linewidths (approximately-less-than)250 MHz in the UV. This spectrum not only displays completely resolved rotational structure, but also fine and hyperfine structure. The hyperfine constants and precise interatomic distances derived from the rotational constants provide a very interesting picture of the electronic and geometric structure of the complex. The bonding is incipiently chemical in the A˜ state with clear evidence for at least some electronic reorganization between Ar and the open-shell OH radical in the complex. Conversely, the X˜ state appears to be bound almost solely by physical van der Waals interactions characteristic of systems containing only closed-shell species.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.461437
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  • 2
    Electronic Resource
    Electronic Resource
    High resolution electronic spectroscopy of Ne⋅OH (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 3476-3483 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The high resolution electronic spectrum of Ne⋅OH has been recorded in a supersonic free jet expansion using the laser-induced fluorescence technique. From an analysis of the spectrum which yields rotational constants, we are able to obtain Ne⋅OH bond lengths in several vibrational (hindered rotor) levels of the excited state and the vibrationless level of the ground state. We also measure the Fermi contact constant in the A˜ state which is, unlike Ar⋅OH, insignificantly perturbed from the value in the OH monomer. However, we now measure a parity doubling of the X˜ state rotational levels which is tenfold larger than the upper limit we established for such an interaction in Ar⋅OH. We interpret these latter measurements to imply weaker and more isotropic bonding in Ne⋅OH compared to Ar⋅OH in both electronic states.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.461901
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  • 3
    Electronic Resource
    Electronic Resource
    High resolution electronic spectroscopy of Ar⋅OH and Ar⋅OD vibronic bands (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 7999-8008 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Laser-induced fluorescence spectra with resolved rotational, fine, and hyperfine structure have been observed for the U bands of the A˜←X˜ electronic transition of the Ar⋅OH/D complex. The appearance of these spectra are very different from the previously analyzed A band system of the complex. Detailed analysis of the spectra reveals that their spectral differences are caused by changes in values of molecular parameters (due to the different regions of the potential surface sampled in the A˜ state) and their resulting effect upon the coupling of the angular momenta in the complex. Numerical results are given for the molecular parameters in the A˜ state levels examined in these experiments and the implication of these values for the geometry and the potential surface of the complex are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.463423
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  • 4
    Electronic Resource
    Electronic Resource
    Electronic spectroscopy and excited state dynamics of the Ar⋅SH complex (1993)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 4301-4304 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The laser excitation spectrum A˜ (0,00,vS')−X˜ (0,00,0), has been observed for the Ar⋅SH complex. Rotational constants and bond lengths have been obtained for vibrational levels of the A˜ and X˜ states. A remarkable lengthening of the A˜ state natural lifetime is observed upon Ar complexation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.465037
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  • 5
    Electronic Resource
    Electronic Resource
    Frequency-modulation transient absorption spectrum of the HCCl A˜1A′′(0,0,0)←X˜1A′(0,0,0) transition (1995)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 102 (1995), S. 6347-6353 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The rotationally resolved spectrum of the HCCl A˜1A′′(0,0,0)←X˜1A′(0,0,0) transition between 12 230 and 12 410 cm-1 was obtained for the first time at Doppler-limited resolution using a frequency-modulation (FM) transient absorption technique. Five major subbands (Ka=0←1, 1←0, 1←2, 2←1, and 2←3) of HC35Cl and one subband (Ka=0←1) of HC37Cl were observed and assigned. In addition, the forbidden subband (Ka=0←0) of HC35Cl was also observed. Thus far, we have assigned most (more than 70%) of the strong lines. The analysis of these subbands determines the geometry for the HCCl A˜(0,0,0) level: (angle)HCCl=134.7° and RC-Cl=1.623 Å while RC-H is fixed at the corresponding value of CH2. The height of the barrier to linearity was found to be approximately 2170 cm-1 above the vibrationless level of the A˜ state. The rotational structure of this spectrum shows irregular perturbations. Both random and J-dependent (anomalous K-type doubling) effects were observed. As in methylene, the perturbations most likely arise from Renner-Teller effect between the two singlet states in combination with spin–orbit coupling between the singlet and triplet states. © 1995 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.1703016
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  • 6
    Electronic Resource
    Electronic Resource
    Near-infrared vibronic spectrum of the CH2 b˜ 1B1←a˜ 1A1 transition (1994)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 9236-9245 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.468015
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  • 7
    Electronic Resource
    Electronic Resource
    High resolution near-infrared electronic spectroscopy of HCBr (1996)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 105 (1996), S. 2135-2140 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The rotationally resolved spectrum of the HCBr A˜ 1A″(0,2,0)←X˜ 1A′(0,0,0) Ka=0←1 transition between 12760 and 12850 cm−1 was obtained for the first time at Doppler-limited resolution using a transient frequency-modulation absorption technique. Rotational structure of HC 79Br and HC 81Br was identified and analyzed. The analysis shows R″(C–Br)=1.852 A(ring) and R′(C–Br)=1.749 A(ring). The observed band indicates a linear–bent transition. This yields an upper limit of approximately 1600 cm−1 for the barrier to linearity above the zero-point energy for the A˜ 1A″ state. Perturbations caused by singlet–triplet interactions were also found in the observed spectrum. The analysis of these perturbations indicates a very low-lying a˜ 3A″ state. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.472086
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  • 8
    Electronic Resource
    Electronic Resource
    Laser excitation and dispersed fluorescence spectra of the HCBr A˜–X˜ vibronic transition (2001)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 115 (2001), S. 766-770 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We recorded the laser-induced fluorescence (LIF) excitation spectra of several HCBr A˜–X˜ vibronic transitions between 580 nm and 630 nm in a direct current (DC) discharge supersonic free jet expansion. Dispersed fluorescence spectra, following excitation of these HCBr A˜–X˜ vibronic transitions were successfully obtained for the first time. The analysis of the dispersed fluorescence spectra reveals the details of the vibrational structure of the X˜ 1A′ state as well as that of the a˜ 3A″ state. The vibrational frequencies were determined as 1119 cm−1 (bend), 676 cm−1 (C–Br stretch) for the X˜ 1A′ state and 994 cm−1 (bend), 733 cm−1 (C–Br stretch) for the a˜ 3A″ state. In addition, based upon the observation of the triplet state levels, the value of the triplet–singlet energy gap (the zero-point level energy gap) could be extracted from the dispersed fluorescence spectra and is to be approximately 2006±8 cm−1 (5.73±0.02 kcal/mol). © 2001 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.1379583
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  • 9
    Electronic Resource
    Electronic Resource
    Experimental study of the DCCl X˜1A′ state vibrational structure by dispersed fluorescence spectroscopy (2002)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 117 (2002), S. 3263-3268 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Dispersed fluorescence spectra following excitation of the DCCl A˜-X˜ vibronic bands between 570 and 620 nm were successfully recorded for the first time using a combination of direct current discharge and supersonic free jet expansion techniques to produce the radical. This is the first experimental study on the DCCl X˜1A′ state vibrational structure. Analysis of the dispersed fluorescence spectra reveals details of the vibrational structure of the DCCl X˜1A′ state. Emission bands to all three vibrational modes were observed and the fundamental vibrational frequencies were determined: 2078 cm−1 (C–D stretch), 893 cm−1 (bend), and 801 cm−1 (C–Cl stretch). Vibrational parameters including anharmonicities and the bend-stretch coupling constant for the DCCl X˜1A′ state were also determined using a least-square fit. In addition, based on our results, the triplet-singlet energy gap (the zero-point level energy gap) could be estimated to be approximately 11±2 kcal/mol. © 2002 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.1485768
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  • 10
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    Spectroscopic Investigation of the Multiphoton Photolysis Reactions of Bromomethanes (CHBr3, CHBr2Cl, CHBrCl2, and CH2Br2) at Near-Ultraviolet Wavelengths† (2010)
    American Chemical Society
    Details
    Publication Date: 2010-04-15
    Print ISSN: 1089-5639
    Electronic ISSN: 1520-5215
    Topics: Chemistry and Pharmacology , Physics
    Published by American Chemical Society
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