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At least 37 records · Page 2

Dipole moments and transition probabilities of the a 3Sigma(+)g - b 3Sigma(+)u system of molecular hydrogen

Multiconfiguration variational calculations of the electronic wave functions of the a 3Sigma(+)g and b 3Sigma(+)u states of molecular hydrogen are presented, and the electric dipole transition moment between them (of interest in connection with stellar atmospheres and the UV spectrum of the Jovian planets) is obtained. The dipole moment is used to calculate the probabilities of radiative transitions from the discrete vibrational levels of the a 3Sigma(+)g state to the vibrational continuum of the repulsive b 3Sigma(+)u state as functions of the wavelength of the emitted photons. The total transition probabilities and radiative lifetimes of the levels v prime = 0-20 are presented.

Guberman, S.↗

Molecular processes in comets

The transition dipole moments of the c 3 Pi u - a 3 Sigma g +, i 3 Pi g - c 3 Pi u, and i 3 Pi g - b 3 Sigma u + transitions of molecular hydrogen were calculated over a wide range of internuclear distances R. Calculations of the emission spectra are nearing completion. Substantial progress was made in the calculation of the absorption coefficient of a colliding pair of hydrogen atoms in the binary encounter approximation. Detailed calculations were performed on the continuum emission arising from the excitation of the a 3 sigma g + state of H2 by the impact of electrons of various energies. Each curve is labelled by the electron energy in electron volts. The strong emission near Lyman alpha is interesting in that it is produced by excitation of molecular hydrogen.

Dalgarno, A.↗

Isotopologue Consistency of Semi-Empirically Computed InfraRed Line Lists and Further Improvement for Rare Isotopologues: CO2 and SO2 Case Studies.

The semi-empirical molecular rovibrational IR line lists, such as ExoMol, TheoReTs, and Ames, combine the experimental accuracy and theoretical power to reach better than 0.1 cm-1 accuracy for line positions and better than 80-90% agreement for line intensities. The quality of these existing semi-empirical IR lists allows further improvements of intensity and line positions for those unobserved minor isotopologues. This paper presents our new BTRHE (Best Theory + Reliable High-resolution Experiment) strategy implementation. For line intensity, the isotopologue consistency and the patterns of mass dependence in the Ames-296K SO2 and CO2 IR lists are quantitatively presented along the mass-inverse coordinates. The consistency and patterns are better than those in existing experimental data. The methodology proposed here can be used to identify inconsistencies, outliers, and mistakes in intensities, and help improve Effective Dipole Model (EDM) and molecular IR databases. We call for an experimental study on the 50006 and 60007 bands of CO2 628. For line position predictions, a simple approach combining the variational IR line lists with Effective Hamiltonian (EH) model may refine the effective rotational constants A0/B0/C0 and quartic centrifugal distortion constants of minor isotopologues. The prediction accuracy may be improved by two orders of magnitude, i.e. reaching 0-5 MHz prediction accuracy in the range of J<20-30, Ka<10-20, and 0.01-0.02 MHz accuracy for A0/B0/C0. Several important factors have been systematically investigated and discussed, e.g. convergence, uncertainties, higher order terms, fixing EH parameters, mass coordinates, etc. Amicrowave (MW) line set consisting of 644,636 strong transitions for all 30 isotopologues and corresponding refined EH(Ames) parameters are reported in the supplementary material. This approach may be easily extended to rovibrational bands, hot bands, and other molecular systems.

Xinchuan Huang↗

Substituent and Solvent Effects on Excited State Charge Transfer Behavior of Highly Fluorescent Dyes Containing Thiophenylimidazole-Based Aldehydes

The excited state charge transfer for a series of highly fluorescent dyes containing thiophenylimidazole moiety was investigated. These systems follow the Twisted Intramolecular Charge Transfer (TICT) model. Dual fluorescence was observed for each substituted dye. X-ray structures analysis reveals a twisted ground state geometry for the donor substituted aryl on the 4 and 5 position at the imidazole ring. The excited state charge transfer was modeled by a linear solvation energy relationship using Taft's pi and Dimroth's E(sub T)(30) as solvent parameters. There is linear relation between the energy of the fluorescence transition and solvent polarity. The degree of stabilization of the excited state charge transfer was found to be consistent with the intramolecular molecular charge transfer. Excited dipole moment was studied by utilizing the solvatochromic shift method.

Santos, Javier↗

Dipole moments and transition probabilities of the i 3Pi sub g-b 3Sigma(+) sub u, c 3Pi sub u-a 3Sigma(+) sub g, and i 3Pi sub g-c 3Pi sub u systems of molecular hydrogen

Bonn-Oppenheimer-based ab initio calculations of dipole moments from the i 3Pi sub g-b 3Sigma(+) sub u, c 3Pi sub u-a 3Sigma(+) sub g, and i 3Pi sub g-c 3Pi sub u transitions of H2 have been conducted, to yield a tabulation of the dipole transition probabilities and Franck-Condon factors. These factors are given for transitions originating in the lowest vibrational level of the ground X 1Sigma(+) sub g state.

Guberman, Steven L.↗

Laboratory millimeter and submillimeter spectra of CO/+/

The strong electric dipole-allowed transitions of the molecular ion CO(+) in the region 235-470 GHz have been measured in the laboratory. The laboratory spectra at 235 GHz appear to confirm the claim by Erickson et al. (1981) to have observed CO(+) in OMC-1.

Sastry, K. V. L. N.↗

Photoabsorption in formaldehyde

Theoretical studies of the vertical electronic dipole excitation and ionization spectra in molecular formaldehyde are reported. The investigations relied on configuration-interaction calculations and moment-theory techniques. A double-zeta basis of contracted Gaussian-lobe functions supplemented with appropriate polarization and bond functions was used to construct Fock spectra in C(2 nu) symmetry for certain states near the ground state equilibrium geometry. The ionization energies, discrete vertical transition frequencies, and oscillator strengths for occupied and vertical Fock orbitals are in general accord with experimental determinations and other theoretical calculations. Stieltjes and Chebyshev vertical electronic photoionization profiles were calculated and found to be in good agreement with appropriately averaged photoionization-mass spectrometric measurements of the cross section for parent H2CO(+) ion production.

Langhoff, P. W.↗

Aeolian Sand Transport in the Planetary Context: Respective Roles of Aerodynamic and Bed-Dilatancy Thresholds

The traditional view of aeolian sand transport generally estimates flux from the perspective of aerodynamic forces creating the airborne grain population, although it has been recognized that "reptation" causes a significant part of the total airborne flux; reptation involves both ballistic injection of grains into the air stream by the impact of saltating grains as well as the "nudging" of surface grains into a creeping motion. Whilst aerodynamic forces may initiate sand motion, it is proposed here that within a fully-matured grain cloud, flux is actually governed by two thresholds: an aerodynamic threshold, and a bed-dilatancy threshold. It is the latter which controls the reptation population, and its significance increases proportionally with transport energy. Because we only have experience with terrestrial sand transport, extrapolations of aeolian theory to Mars and Venus have adjusted only the aerodynamic factor, taking gravitational forces and atmospheric density as the prime variables in the aerodynamic equations, but neglecting reptation. The basis for our perspective on the importance of reptation and bed dilatancy is a set of experiments that were designed to simulate sand transport across the surface of a martian dune. Using a modified sporting crossbow in which a sand-impelling sabot replaced the bolt-firing mechanism, individual grains of sand were fired at loose sand targets with glancing angles typical of saltation impact; grains were projected at about 80 m/s to simulate velocities commensurate with those predicted for extreme martian aeolian conditions. The sabot impelling method permitted study of individual impacts without the masking effect of bed mobilization encountered in wind-tunnel studies. At these martian impact velocities, grains produced small craters formed by the ejection of several hundred grains from the bed. Unexpectedly, the craters were not elongated, despite glancing impact; the craters were very close to circular in planform. High-speed photography showed them to grow in both diameter and depth after the impactor had ricochetted from the crater site. The delayed response of the bed was "explosive" in nature, and created a miniature ejecta curtain spreading upward and outward for many centimeters for impact of 100-300 micron-diameter grains into similar material. Elastic energy deposited in the bed by the impacting grain creates a subsurface stress regime or "quasi-Boussinesq" compression field. Elastic recovery of the bed occurs by dilatancy; shear stresses suddenly convert the grains from closed to open packing, and grains are consequently able to eject themselves forcefully from the impact site. Random jostling of the grains causes radial homogenization of stress vectors and a resulting circular crater. There is a great temptation to draw parallels with cratering produced by meteorite impacts, but a rigorous search for common modelling ground between the two phenomena has not been conducted at this time. For every impact of an aerodynamically energized grain, there are several hundred grains ejected into the wind for the high-energy transport that might occur on Mars. Many of these grains will themselves become subject to the boundary layer's aerodynamic lift forces (their motion will not immediately die and add to the creep population), and these grains will become indistinguishable from those lifted entirely by aerodynamic forces. As each grain impacts the bed, it will eject even more grains into the flow. A cascading effect will take place, but because it must be finite in its growth, damping will occur as the number of grains set in motion causes mid-air collisions that prevent much of the impact energy from reaching the surface of the bed -thus creating a dynamic equilibrium in a high-density saltation cloud. It is apparent that for a given impact energy, the stress field permits a smaller volume of grains to convert to open packing as the size of the bed grains increases, or as the energy of the "percussive" grain decreases (by decrease in velocity or mass). Thus, the mass of the "repercussive" grain population that is ejected from the impact site becomes a function of the scale of the stress field in relation to the scale of the bed material (self-similarity being applicable if both bed size and energy are simultaneously adjusted). In other words, in a very high energy aeolian system where an aerodynamically raised grain can ballistically raise many more grains, the amount of material lifted into the wind becomes largely a function of a dilatancy threshold. If this threshold is exceeded, grains are repercussively injected into the saltation cloud. The "dilatancy threshold" may be defined in terms of the saltation percussive force required to convert the bed, through elastic response, from a closed to an open packing system. If open packing cannot be created, the grains cannot escape from the impact site, even though the elastic deformation and percussive force may be able to reorganize the grains with respect to one another. As the crossbow experiments showed, for an ever-increasing bed grain size, a point is reached when no material can be moved because the energy of the percussive grain is insufficient to dilate the relatively coarse bed. Although this seems to be stating the obvious -- that too little energy will not cause the bed to splash -- the consequences of exceeding the "splash threshold" by dilatancy are not so obvious for high-energy aeolian transport. It is noted that the force required to elastically dilate the bed has to overcome Coulombic grain attractions such as dipole-dipole coupling, dielectric, monopole, contact-induced dipole attractions, van der Waals forces, molecular monolayer capillary forces, as well as the mechanical interlocking frictional resistance of the grains. On Mars, it is predicted that the dilatancy threshold may be the prime control of grain flux. Additional information is contained in the original.

Marshall, J. R.↗

Transition probabilities of the B-prime 1Sigma(u)(+) to X 1Sigma(g)(+) system of molecular hydrogen

From published potential energy curves and transition dipole moments, there are obtained by numerical integration of the equations of nuclear motion the vibrational eigenfunctions of the X 1Sigma(g)(+) and B-prime 1Sigma(u)(+) states of H2. The probabilities of radiative transitions from the discrete vibrational levels of the excited B-prime 1Sigma(u)(+) electronic state of H2 to the discrete and continuum vibrational levels of the ground X 1Sigma(g)(+) electronic state are calculated. The Franck-Condon factors are also presented.

Kwok, T. L.↗

Dielectric Properties of Piezoelectric Polyimides

Molecular modeling and dielectric measurements are being used to identify mechanisms governing piezoelectric behavior in polyimides such as dipole orientation during poling, as well as degree of piezoelectricity achievable. Molecular modeling on polyimides containing pendant, polar nitrile (CN) groups has been completed to determine their remanent polarization. Experimental investigation of their dielectric properties evaluated as a function of temperature and frequency has substantiated numerical predictions. With this information in hand, we are then able to suggest changes in the molecular structures, which will then improve upon the piezoelectric response.

Ounaies, Z.↗

Modeling of pressure-induced far-infrared absorption spectra Molecular hydrogen pairs

Meyer et al. (1985) have calculated the accurate induced dipole moment function of H2-H2 from first principles, using highly correlated wave functions for the first time in such work. The present paper is concerned with the collision-induced translational-rotational absorption coefficient for molecular hydrogen pairs, taking into account computations on the basis of the fundamental theory considered by Meyer et al. Data have been obtained for temperatures in the range from 40 to 300 K. Criteria are developed for choosing among various model line shapes. It is found that certain models are capable of approximating the quantum profiles closely, with rms errors of only a few percent.

Borysow, J.↗

Angular motion of a PAH molecule in interstellar environment

Polycyclic aromatic hydrocarbon (PAH) molecules have recently been proposed as an important and hitherto undetected component of the Interstellar Medium (ISM). The theory was based on an explanation of the Unidentified IR Emission Bands by Leger et al. It has already led to a verified prediction on extended galactic and extragalactic emissions measured by IRAS, or by a recent balloon borne experiment. The physics that rules the motion of such molecules in the ISM was studied, taking into account their coupling with the ambient gas, the radiation field (absorption and emission) and the static magnetic field. This is important for many implications of the PAH theory such as the radio emission by these molecules or the expected polarization of their IR emission. A reflection nebulae is considered where the situation is rather well known. Every day life of a mean PAH molecule in such a region is as follows: every 3 hrs a UV photon is absorbed heating the molecule to a thousand degs; the temperature decay due to cooling by IR emission follows then within a few seconds. A collision with a molecule of gas occurs typically once a week, while an H atom is ejected or captured at the same rate. A typical cooling cycle after a heat impulse is given. The PAH molecules studied as representative of the family has typically 50 atoms, a radius of 4.5 A, is circular and has a molecular mass of M = 300; its permanent dipole moment is 3 Debye.

Rouan, D.↗

Electron-impact excitation of the a3Sigma(+)g, B1Sigma(+)u, c3Pi u, and C1Pi u states of H2

Normilized differential and integral cross sections for electron-impact excitation of the dipole-allowed B1Sigma(+)u, C1Pi u and dipole-forbidden a3Sigma(+)g, c3Pi u states of molecular hydrogen have been determined by analysis of energy-loss spectra obtained with a crossed-beam apparatus at electron-impact energies of 20, 30, 40 and 60 eV and scattering angles ranging from 10 to 120 degrees. Normalization of the data was achieved by utilizing elastic differential cross sections measured previously by (Khakoo and Trajmar, 1986). The cross sections are compared with other available theoretical and experimental data.

Khakoo, M. A.↗