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  • 1
    Electronic Resource
    Electronic Resource
    Photodissociation of hydrogen sulfide at 157.6 nm: Observation of SH bimodal rotational distribution (1999)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 3940-3945 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Photodissociation of the H2S molecule at 157.6 nm was studied experimentally using the Rydberg tagging technique. Translational energy distributions of the H-atom product from the H2S photodissociation were measured, and the SH(X 2Π)+H(2S) channel was found to be the dominant dissociation process. Spin-orbit and rovibrational state distributions were also obtained for the SH product, which was found to be both vibrationally and rotationally excited. An intriguing bimodal rotational distribution in the lowest two vibrational states, v=0 and 1, has been clearly observed for the SH product, indicating that there are two distinctive dissociation mechanisms involved in the photodissociation of H2S at 157 nm excitation. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.479736
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  • 2
    Electronic Resource
    Electronic Resource
    Efficient state-specific preparation of highly vibrationally excited NO(X 2Π) (1990)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 116-120 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Vibrational levels of nitric oxide (NO) X 2Π from v‘=8–24, whose energies vary from 1.76 to 4.61 eV, have been produced using the stimulated emission pumping (SEP) technique. A narrowband tunable argon fluoride laser is used to access the B 2Π state which provides good Franck–Condon overlap with many vibrational levels of the ground electronic state. Saturation of the transitions is achieved at low pulse energies providing high pumping efficiency. Both spin–orbit states of NO are accessible with this scheme. Accurate molecular constants for v‘=23 and 24 are given for the first time. The feasibility of an optically pumped infrared laser is discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.458480
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  • 3
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism studies of switching and association reactions involving Na+–ligand complexes (1990)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 2405-2412 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The kinetics and mechanisms of the reactions of Na+⋅(X)n=0–3, X=water, ammonia, and methanol with CH3CN, CH3COCH3, CH3CHO, CH3COOH, CH3COOCH3, NH3, CH3OH, and CH3–O–C2H4–O–CH3(DMOE) were studied at ambient temperature under different pressures. All of the switching (substitution) reactions proceed at near-collision rate and show little dependence on the flow tube pressure, the nature and size of the ligand, or the type of core ions. Interestingly, all of the measured rate constants agree well with predictions based on the parametrized trajectory calculations of Su and Chesnavich [J. Chem. Phys. 76, 5183 (1982)]. The reactions of the bare sodium ion with all neutrals proceed via a three-body association mechanism and the measured rate constants cover a large range from a slow association reaction with NH3, to a near-collision rate with DMOE. The lifetimes and the dissociation rate constants of the intermediate complexes deduced using the parametrized trajectory results, combined with the experimentally determined rates, compare fairly well with predictions based on RRKM theory. The calculations also account for the large isotope effect observed for the clustering of ND3 and NH3 to Na+.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.459021
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  • 4
    Electronic Resource
    Electronic Resource
    A study of the structure and dynamics of the hydronium ion by high resolution infrared laser spectroscopy. III. The ν3 band of D3O+ (1990)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 3257-3260 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: 294 transitions were measured by velocity modulation spectroscopy using a difference frequency laser system with a D2/O2 discharge and assigned to the ν3 (antisymmetric stretch) band of D3O+. A simultaneous analysis of this data with the ν2 band spectra reported by Sears, et al. [J. Chem. Phys. 83, 2676 (1985)] yielded a refined set of parameters for both the ground and the excited states of both bands. The ν3 bandcenters are 2629.6512(39) and 2624.2376(47) cm−1 for the s–s and a–a inversion components, respectively.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.457884
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  • 5
    Electronic Resource
    Electronic Resource
    The potential energy function for O2 X(3∑−g ) and the transition dipole moment of the Schumann–Runge band near X-state dissociation (1989)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 7114-7117 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Emission spectra were analyzed for transitions of O2 (B 3∑−u, v'→X 3∑−g, v‘) with v‘ as high as 35. The X 3∑−g potential energy function, Vx (r), was determined nearly to the dissociation limit with an estimated accuracy of ±50 cm−1. Vx (r) is compared to the highest level ab initio calculation available. The transition dipole moment function, μ(r), for the O2 Schumann–Runge band is also extended almost to the dissociation limit. The O2 molecule now provides one of the best testing grounds for ab initio theories of dissociation and radiation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.456240
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  • 6
    Electronic Resource
    Electronic Resource
    Spectroscopic characterization of mesogen order in discotic liquid crystal (1988)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 5950-5955 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Infrared and Raman spectra of the discotic liquid crystal molecules benzene–hexa-hexanoate (BH6), benzene–hexa-heptanoate (BH7), benzene–hexa-octanoate (BH8), and benzene–hexa-nananoate (BH9), and of mixtures of BH7 with BH8, are reported as a function of temperature. The 1615 cm−1 infrared band is strong in the Raman spectrum of BH7 and is taken as a characteristic of and diagnostic for central core disorder in all these molecules and mixtures. The aliphatic side chains are shown to disorder at much lower temperatures than the central core, and order in the central core is shown to remain throughout the liquid crystalline region.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.455546
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  • 7
    Electronic Resource
    Electronic Resource
    Studies of the energy dependence of reactions of Ar+ and Ar+2 with CH4 and CS2 (1987)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 1630-1636 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The rate coefficients for the reactions of Ar+ and Ar+2 with CH4 and CS2 are obtained as a function of energy by using a selected ion flow tube with an electric drift field (SIFT-DRIFT). A diagnostic analysis of the system and technique has been completed and allows rate coefficients to be reported with a high level of confidence. Rate coefficients and product branching ratios are determined for the methane reactions from thermal (room temperature) to center-of-mass kinetic energies of about 0.15 eV and for the carbon disulfide reactions from thermal to about 0.6 eV. The overall rate coefficients for these reactions do not vary a great deal over the investigated energy range. The greatest dependence is found for the slowest reaction Ar+ with CS2, where a minimum in the rate coefficient is observed near 0.15 eV. The behavior of the branching ratios for S+ and CS+2 suggests curve crossings between a repulsive state and the A, B, and C electronic states of CS+2.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.453224
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  • 8
    Electronic Resource
    Electronic Resource
    Dissociation dynamics of the water molecule on the A˜ 1B1 electronic surface (2000)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 10597-10604 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Photodissociation of H2O, D2O, and HOD on the A˜ 1B1′ surface through 157.6 nm excitation has been studied using the H(D) atom Rydberg tagging time-of-flight technique. Vibrational state distribution has been measured for the OH/OD product from the photodissociation of the H2O, D2O, and HOD molecules. Comparisons of our results with previous theoretical calculations and experimental results obtained using the laser induced fluorescence (LIF) technique have been made. Experimental results in this work indicate that the relative populations for vibrationally excited OH(v≥2) products measured using LIF are significantly underestimated, suggesting that LIF as a technique to quantitatively measure vibrational distributions of reaction product OH is seriously flawed. The experimental results presented here are in rather good agreement with previous theoretical calculations. However, our results indicate that the calculated vibrational populations for the higher vibrational states of OH are still somewhat overestimated. Relative branching ratio of H and D productions from HOD has also been estimated. This complete set of data for the photodissociation of H2O should provide an excellent testing ground for improving the theoretical potential energy surface of the first electronically excited state of the water molecule. © 2000 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.1285899
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  • 9
    Electronic Resource
    Electronic Resource
    Temperature dependence of ion pairing of a potassium salt in nonaqueous liquid and polymer electrolytes: X-ray absorption studies (1994)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 3230-3233 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Near-edge x-ray absorption fine structure spectroscopy was used to study the effect of temperature on ion pairing of a potassium salt in a modified carbonate (MC3) solution and in a poly(ethylene oxide)-potassium salt complex that used MC3 as a plasticizer. The modified carbonate was made by attaching three ethylene oxide units to the four position of ethylene carbonate. Spectra were obtained, at the K edge of potassium, over the temperature range of 25–110 °C. Studies of reference systems showed a correlation between ion pairing and white line splitting in the near-edge region of the spectra. The degree of white line splitting was used as a qualitative indicator of the degree of ion pairing as a function of temperature. The results indicate that, in both systems, the number of ion pairs increases with increasing temperature.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.467569
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  • 10
    Electronic Resource
    Electronic Resource
    Sub-Doppler infrared spectroscopy of HCCCN–BF3 (v1) and HCN–BF3 (v1 and 2v1) (1994)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 2762-2771 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Using a molecular beam opthothermal spectrometer, we have recorded the sub-Doppler ir rovibrational spectra of the CH stretching vibrations of the C3v symmetric-top van der Waals molecules HCCCN–BF3 (v1 fundamental) and HCN–BF3 (v1 fundamental and first overtone). At first sight, all spectra appear regular, showing no signs of extensive (local) perturbations as might have been expected from the similarities in structure between HCN–BF3 and the stable molecule HCCCF3, of which the 2v1 spectrum in particular presents a clear example of intermediate case intramolecular vibrational energy relaxation. However, closer inspection reveals that the HCCCN–BF3 spectrum shows evidence of an isotope dependent vibrational predissociation rate, the 11B complex dissociating at least twice as fast as its 10B counterpart. The complexation induced red shift equals 2.70 cm−1, and is in the same range as observed for the majority of the HCCCN and HCN complexes studied to date. In contrast, the HCN–BF3 spectra show instrument limited linewidths, therewith providing only a lower limit to the lifetime, but the complexation induced frequency shifts are clearly anomalous: the fundamental spectrum is red shifted by only 0.15 cm−1, while the overtone spectrum is blue shifted by 0.66 cm−1. These observations are rationalized by invoking long-range (anharmonic) vibrational interactions in both the HCCCN–BF3 and the HCN–BF3 molecule.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.468472
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