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  • American Institute of Physics (AIP)  (142)
  • American Geophysical Union (AGU)
  • 2005-2009
  • 1990-1994  (142)
  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 3427-3431 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Flow of fluids confined in molecularly narrow pores is studied by molecular dynamics. Strong density variations across the pore render the usual dependence of the local viscosity on local density inappropriate. At separations greater than four molecular diameters flow can be described by a simple redefinition of local viscosity. In narrower pores a dramatic increase of effective viscosities is observed and is due to the inability of fluid layers to undergo the gliding motion of planar flow. This effect is partially responsible for the strong viscosity increases observed experimentally in thin films that still maintain their fluidity.
    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 92 (1990), S. 4308-4319 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Means are presented for using stationary points in two ways. One, for well-understood potentials, elucidates relations between the form of the surface and the dynamics that it supports, including the determination of the effective molecular symmetry group. The other, for potentials of uncertain quality, provides a test for unphysical characteristics and suggests how the surface might be improved if it is found to be unsatisfactory in some respect. Our approach involves comparison of transition state calculations using the slowest slide and Cerjan–Miller algorithms for two example systems: the Lennard-Jones Ar7 cluster and the Handy–Carter many-body-expansion potential for the ground state of formaldehyde.
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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. 1720-1731 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Electronic quenching of BrCl B 3Π(O+) was studied in pulsed and steady-state laser induced fluorescence experiments. BrCl(B) deactivation rate coefficients were determined as a function of vibrational quantum number for the following collision partners: He, Ne, Ar, Kr, N2, O2, and Cl2. Quenching from a vibrationally thermalized, 300 K BrCl(B,v') distribution by the noble gases N2, and Cl2 was slow with all rate coefficients less than 4.3±0.7×10−13 cm3 molecule−1 s−1 . The quenching by O2 was much faster with a rate coefficient of 6.5±0.6×10−12 cm3 molecule−1 s−1 . The quenching of BrCl(B), under single collision conditions, depends strongly on vibrational quantum number of BrCl(B), with rate coefficients ranging from 4.3±0.1×10−13 cm3 molecule−1 s−1 for v'=0 to 1.4±0.3×10−10 cm3 molecule−1 s −1 for v'=6 under collisions with Cl2 and with rate coefficients ranging from 1.5±0.3×10−13 cm3 molecule−1 s−1 for v'=0 to 1.0± 0.4×10−10 cm3 molecule−1 s−1 for v'=6 under collisions with He. Several mechanisms for the electronic deactivation of BrCl(B) are discussed. The radiative lifetime of BrCl(B) was determined to be 38.7±1.7 μs, independent of vibrational level for v'≤6.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 5087-5098 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We construct a free-energy density-functional approximation for the primitive model of the electrical double layer. The hard-sphere term of the free-energy functional is based on a nonlocal generic model functional proposed by Percus. This latter model functional, which is a generalization of the exact solution for the nonuniform hard-rod model, requires as input the free energy of a homogeneous hard-sphere mixture. We choose the extension of the Carnahan–Starling equation of state to mixtures. The electrostatic part of the nonuniform fluid ion–ion correlations present in the interface is approximated by that of a homogeneous bulk electrolyte. Using the mean spherical approximation for a neutral electrolyte, we apply the theory to symmetrical 1:1 and 2:2 salts in the restricted primitive model. We present comparisons of density profiles and diffuse layer potentials with Gouy–Chapman theory and Monte Carlo data. We also compare our results with data from other recent theories of the double layer. For highly charged surfaces, the profiles show the layering of counterions and charge inversion effects, in agreement with Monte Carlo data.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 4479-4489 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Nonlocal density functional free energy theories are used to investigate the nature of the wetting transition of a Lennard-Jones fluid near a Lennard-Jones wall. In particular, the wetting behavior is investigated for argon films on a solid carbon dioxide substrate for which the Lennard-Jones parameters are known. In accordance with previous predictions of local density functional theories, the transition is found to be of first order. The locus of the prewetting line of the Ar–CO2 system is calculated. Density profiles obtained from the Tarazona and generalized hard rod models are both in qualitative agreement with Monte Carlo simulations of Finn and Monson, although Tarazona's model performs better quantitatively.
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 4339-4344 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The density distribution functions of a confined one-dimensional fluid of particles obeying the Tonks–Takahashi nearest neighbor two-body potential are reduced to simple functions of the grand canonical ensemble partition function. The resulting formulas are analogous to those found by Robledo and Rowlinson for a hard-rod fluid. In the absence of an external field the partition functions can be evaluated by the method of Laplace transforms. The dependence of the pressure P on the separation L of the confining walls is investigated for three model potentials: (i) hard rod, (ii) square well, and (iii) triangle well. P is an oscillating function of L in all three cases. The oscillations arise from the ordering effect of the repulsive forces between particles. The attractive interactions of the triangle-well potential reinforces the ordering whereas those of the square-well potential diminishes the ordering. Results for semiconfined and homogeneous fluids are also presented.
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 1661-1671 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A cw laser-induced fluorescence experiment is described in which state-to-state rate coefficients for rotation-to-translation energy transfer have been determined from J'=72, v'=6 in IF B 3Π(0+). Using the collision partners He, Ne, Ar, Kr, Xe, N2, and CF4, nearly 500 individual rate coefficients have been measured. The rare-gas atoms display a characteristic behavior with the heavier collision partners more efficiently exchanging large amounts of angular momentum in a single collision.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 4809-4818 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Laser induced fluorescence spectra of expansion-cooled NO2/Ne samples (1 and 2 K) are reported for transitions that originate from the lowest rovibronic levels and terminate on levels near D0. At 1 K, nearly all transitions originate from N‘=0. With the present resolution of 0.02 cm−1, the 1 K spectra are resolved rather well. The high density of transitions is due to couplings between rovibronic levels with different N and K quantum numbers and with electronic characters that borrow oscillator strength from bright B2 vibronic species of the mixed 2A1/2B2 electronic system. Just above reaction threshold, such rovibronic species comprise the manifold of levels sampled by optically prepared wave packets. However, at higher energies we argue that the density of B2 vibronic species is a more relevant parameter to describe the nature of unimolecular reactions. Nuances of the optical excitation process are discussed.
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 3414-3414 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 2642-2643 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A hierarchical analysis of the 3ν2 band of propyne shows that there are distinct tiers of states and demonstrates that the major avenue for vibrational mixing is anharmonic coupling for K'=0 up to a time of approximately one ns.
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