A study of the distribution of molecules under free molecular flow conditions after collisions with simple geometries
Molecular distribution under free molecular flow conditions within surfaces of simple geometries
SURFACE GEOMETRY↗
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H-H, C-H, and C-C NMR spin-spin coupling constants calculated by the FP-INDO method for aromatic hydrocarbons
The FP-INDO (finite perturbation-intermediate neglect of differential overlap) method is used to calculate the H-H, C-H, and C-C coupling constants in hertz for molecules of six different benzenoid hydrocarbons: benzene, naphthalene, biphenyl, anthracene, phenanthrene, and pyrene. The calculations are based on both the actual and the average molecular geometries. It is found that only the actual molecular geometries can always yield the correct relative order of values for the H-H coupling constants. For the calculated C-C coupling constants, as for the calculated C-H coupling constants, the signs are positive (negative) for an odd (even) number of bonds connecting the two nuclei. Agreements between the calculated and experimental values of the coupling constants for all six molecules are comparable to those reported previously for other molecules.
Long, S. A. T.↗
Structure, vibrational spectrum, and energetics of the CH5(+) ion - A theoretical investigation
Analytic derivative techniques are utilized to determine molecular geometries, vibration spectra, molecular force field, proton affinity, and energetics of clustering of protonated methane. It is observed that the geometries are gradient optimized, while the harmonic force fields and IR intensities are also determined analytically at the SCF level. It is determined that the frequency of the torsional model for rotation of the H2 about the pseudothreefold axis of the CH3(+) group is extremely low, and the proton affinity of CH4 is calculated as 129.0 kcal/mol.
Komornicki, Andrew↗
Calculation of molecular excitation rates
State-to-state collisional excitation rates for interstellar molecules observed by radio astronomers continue to be required to interpret observed line intensities in terms of local temperatures and densities. A problem of particular interest is collisional excitation of water which is important for modeling the observed interstellar masers. In earlier work supported by a different NASA Grant, excitation of water in collisions with He atoms was studied; after many years of successively more refined calculations that problem now seems to be well understood, and discrepancies with earlier experimental data for related (pressure broadening) phenomena are believed to reflect experimental errors. Because of interstellar abundances, excitation by H2, the dominant interstellar species, is much more important than excitation by He, although it has been argued that rates for excitation by these are similar. Under the current grant theoretical study of this problem has begun which is greatly complicated by the additional degrees of freedom which must be included both in determining the interaction potential and also in the molecular scattering calculation. We have now computed the interaction forces for nearly a thousand molecular geometries and are close to having an acceptable global fit to these points which is necessary for the molecular dynamics calculations. Also, extensive modifications have been made to the molecular scattering code, MOLSCAT. These included coding the rotational basis sets and coupling matrix elements required for collisions of an asymmetric top with a linear rotor. A new method for numerical solution of the coupled equations has been incorporated. Because of the long-ranged nature of the water-hydrogen interaction it is necessary to integrate the equations to rather large intermolecular separations, and the integration methods previously available in MOLSCAT are not ideal for such cases. However, the method used by Alexander in his HIBRIDON code is particularly suited for such cases. We have obtained this code and incorporated that part which solves the coupled differential equations as an option in the MOLSCAT program.
Flynn, George↗
Molecular Modeling and Experimental Investigations of Nonlinear Optical Compounds Monosubstituted Derivatives of Dicyanovinylbenzene
A search for potential nonlinear optical compounds was performed using the Cambridge Structure Database and molecular modeling. We investigated a series of monosubstituted derivatives of dicyanovinylbenzene, since the nonlinear optical (NLO) properties of such derivatives (o-methoxy-dicyanovinylbenzene, DIVA) were studied earlier. The molecular geometry of these compounds was investigated with x-ray analysis and discussed along with the results of molecular mechanics and ab initio quantum chemical calculations. The influence of crystal packing on the planarity of the molecules of this series has been revealed. Two new compounds from the series studied, ortho-F and para-Cl-dicyanovinylbenzene, according to powder measurements, were found to be NLO compounds in the crystal state about 10 times more active than urea. The peculiarities of crystal structure formation in the framework of balance between van der Waals and electrostatic interactions have been discussed. The crystal shape of DIVA and two new NLO compounds have been calculated on the basis of the known crystal structure.
Timofeeva, Tatiana V.↗
Condon loci of diatomic molecular spectra
Geometry of diatomic molecular wave functions - molecular spectroscopy
DIATOMIC MOLECULE↗
Molecular Modeling and Experimental Study of Nonlinear Optical Compounds: Mono-Substituted Derivatives of Dicyanovinylbenzene
A search for potential nonlinear optical (NLO) compounds has been performed using the Cambridge Structural Database and molecular modeling. We have studied a series of mono-substituted derivatives of dicyanovinylbenzene as the NLO properties of one of its derivatives (o-methoxy-dicyanovinylbenzene, DIVA) were described earlier. The molecular geometry in the series of the compounds studied was investigated with an X- ray analysis and discussed along with results of molecular mechanics and ab initio quantum chemical calculations. The influence of crystal packing on the molecular planarity has been revealed. Two new compounds from the series studied were found to be active for second harmonic generation (SHG) in the powder. The measurements of SHG efficiency have shown that the o-F- and p-Cl-derivatives of dicyanovinylbenzene are about 10 and 20- times more active than urea, respectively. The peculiarities of crystal structure formation in the framework of balance between the van der Waals and electrostatic interactions have been discussed. The crystal morphology of DIVA and two new SHG-active compounds have been calculated on the basis of their known crystal structures.
Timofeeva, Tatyana V.↗
An ab initio investigation of the structure, vibrational frequencies, and intensities of HO2 and HOCl
The infrared spectral intensities for HOCl and HO2 have been calculated using a new ab initio technique. Theoretical results for the geometries, vibrational frequencies, and the dipole moments of these species are also reported. All of the calculations were performed at the SCF level using near Hartree-Fock quality basis sets. The results for the molecular geometries and the vibrational frequencies are in good agreement with available experimental data. It is believed that the computed intensities are accurate to at least 50%. The results should be helpful in attempts to determine the stratospheric abundance of HOCl and HO2 by in situ infrared spectroscopic measurements.
Komornicki, A.↗
Formation of Ordered Arrays of Proteins on Surfaces
Van der Waals (dispersion) forces contribute to interactions of proteins with other molecules or with surfaces, but because of the structural complexity of protein molecules, the magnitude of these effects is usually estimated based on idealized models of the molecular geometry, e.g., spheres or spheroids. The calculations reported here seek to account for both the geometric irregularity of protein molecules and the material properties of the interacting media. While the latter are found to fall in the generally accepted range, the molecular shape is shown to cause the magnitudes of the interactions to differ significantly from those calculated using idealized models, with important consequences. First, the roughness of the molecular surface leads to much lower average interaction energies for both protein-protein and protein-surface cases relative to calculations in which the protein molecule is approximated as a sphere. These results indicate that a form of steric stabilization may be an important effect in protein solutions. Underlying this behavior is appreciable orientational dependence, one reflection of which is that molecules of complementary shape are found to exhibit very strong attractive dispersion interactions. Although this has been widely discussed previously in the context of molecular recognition processes, the broader implications of these phenomena may also be important at larger molecular separations, e.g., in the dynamics of aggregation, precipitation and crystal growth.
Lenhoff, A. M.↗
Van der Waals Interactions Involving Proteins
Van der Waals (dispersion) forces contribute to interactions of proteins with other molecules or with surfaces, but because of the structural complexity of protein molecules, the magnitude of these effects is usually estimated based on idealized models of the molecular geometry, e.g., spheres or spheroids. The calculations reported here seek to account for both the geometric irregularity of protein molecules and the material properties of the interacting media. Whereas the latter are found to fall in the generally accepted range, the molecular shape is shown to cause the magnitudes of the interactions to differ significantly from those calculated using idealized models. with important consequences. First, the roughness of the molecular surface leads to much lower average interaction energies for both protein-protein and protein-surface cases relative to calculations in which the protein molecule is approximated as a sphere. These results indicate that a form of steric stabilization may be an important effect in protein solutions. Underlying this behavior is appreciable orientational dependence, one reflection of which is that molecules of complementary shape are found to exhibit very strong attractive dispersion interactions. Although this has been widely discussed previously in the context of molecular recognition processes, the broader implications of these phenomena may also be important at larger molecular separations, e.g., in the dynamics of aggregation, precipitation, and crystal growth.
Roth, Charles M.↗
Molecular attenuation and phase dispersion between 40 and 140-GHz for path models from different altitudes
Radio wave propagation in the 40 to 140 GHz band through the first hundred kilometers of the atmosphere is strongly influenced by the microwave spectrum of oxygen (O2-MS). A unified treatment of molecular attenuation and phase dispersion is formulated. Results of molecular physics are translated into frequency, temperature, pressure, and magnetic field dependencies of a complex refractive index. The intensity distribution of the O2-MS undergoes several changes with increasing altitude. The influence of water vapor is discussed. Examples of computer plots are given as a function of altitude for homogeneous, zenith, and tangential path geometries. Molecular resonances of minor atmospheric gases are discussed briefly.
Liebe, H. J.↗
Experimental Investigation of a Constant-Velocity Traveling Magnetic Wave Plasma Engine
The previously reported traveling magnetic wave plasma engine has been redesigned to reduce the high heat loss to the tube walls downstream of the last magnetic-field coil. The present configuration uses a 3-inch-diameter pyrex tube flared out to a 6-inch diameter immediately downstream of the last magnetic-field coil. This configuration has been studied to determine the effects of flared-tube geometry, molecular weight of the propellant, engine length, and use of a ferrite core on the engine performance. Argon and xenon gases were used as propellants. Two engine lengths were tested. One engine was nominally 1-magnetic-wavelength long (4 coils) and the other nominally 2 1/2-magnetic wavelengths long (10 coils). The magnetic wave speed for both of these lengths corresponds to a specific impulse of 4750 seconds. The maximum kinetic efficiency of the 4-coil engine was 10 percent at a specific impulse of 3200 seconds using argon gas and 22.5 percent at 4200 seconds using xenon gas as the propellant.
TRAVELING WAVE↗
High-temperature thermodynamics.
High temperature thermodynamics requiring species and phases identification, crystal structures, molecular geometries and vibrational, rotational and electronic energy levels and equilibrium constants
Margrave, J. L.↗
Torsional potential function of glyoxal
We have shown, using the fact that glyoxal exists in the trans conformer and the pseudo stable cis conformer that a potential function can be calculated which fits the infrared data of the trans conformer and the microwave intensity data of the cis conformer. This potential function was extended to the d sub 1 and d sub 2 analogs. A study of the potential function of 1,3-butadiene using a different molecular geometry than was previously used was undertaken. Results are presented with different possible vibrational assignments and potential functions which would be consistent with the observed infrared and Raman spectra.
Durig, J. R.↗
H-1 NMR study of ternary ammonia-alkali metal-graphite intercalation compounds
For the first-stage ternary ammonia-alkali metal-graphite intercalation compounds M(NH3)(x)C24(x of about 4, M = K, Rb, Cs), three sets of triplet H-1 NMR spectral lines have been observed at various temperatures and orientations due to the H-1 - H-1 and N-14 - H-1 dipolar interactions. The structures of these compounds have been inferred as mobile (liquid-like) intercalant layers of planar M(NH3)4 ions in between the carbon layers. For the intercalated ammonia molecules, the potential barrier is about 0.2 eV and the molecular geometry is very close to the free NH3 in gas phase.
Tsang, T.↗
Relation between bond-length alternation and second electronic hyperpolarizability of conjugated organic molecules
The solvent dependence of the second hyperpolarizability, gamma, of a variety of unsaturated organic compounds has been measured by third harmonic generation at 1907 nanometers. It is seen that the measured gamma is a function of solvent polarity. These solvent-dependent hyperpolarizabilities are associated with changes in molecular geometry from a highly bond-length alternated, polyenelike structure for a formyl-substituted compound in nonpolar solvents, to a cyaninelike structure, with little bond-length alternation, for a dicyanovinyl-substituted compound in polar solvents. By tuning bond-length alternation, gamma can be optimized in either a positive or negative sense for polymethine dyes of a given conjugation length.
Marder, Seth R.↗
Investigation of ramp injectors for supersonic mixing enhancement
A comparative study of wall mounted swept ramp injectors fitted with injector nozzles of different shape has been conducted in a constant area duct to explore mixing enhancement techniques for scramjet combustors. Six different injector nozzle inserts, all having equal exit and throat areas, were tested to explore the interaction between the preconditioned fuel jet and the vortical flowfield produced by the ramp: circular nozzle (baseline), nozzle with three downstream facing steps, nozzle with four vortex generators, elliptical nozzle, tapered-slot nozzle, and trapezoidal nozzle. The main flow was air at Mach 2, and the fuel was simulated by air injected at Mach 1.63 or by helium injected at Mach 1.7. Pressure and temperature surveys, combined with Mie and Rayleigh scattering visualization, were used to investigate the flow field. The experiments were compared with three dimensional Navier-Stokes computations. The results indicate that the mixing process is dominated by the streamwise vorticity generated by the ramp, the injectors' inner geometry having a minor effect. It was also found that the injectant/air mixing in the far-field is nearly independent of the injector geometry, molecular weight of the injectant, and the initial convective Mach number.
Haimovitch, Y.↗
The Rotational Spectrum of Iodine Dioxide, OIO
The rotational spectra of OIO in its ground vibrational and first excited bending states have been observed for the first time. OIO was formed initially from the products of a microwave discharge in O2 passing over molecular iodine and later with greater yield in a DC discharge through a mixture of O2 and I2 vapor. OIO is an asymmetric prolate rotor (kappa = -0.690) with a (sup 2)B(sub 1) electronic ground state. Over 550 ground state transitions and over 160 transitions of the excited bending state have been included in the fits. The resulting parameters are well determined and will be compared to those recently published for OBrO and OClO. These will be interpreted in terms of the molecular geometry, harmonic force field, and electronic structure.
Miller, Charles E.↗