Interacting He and Ar atoms: Revised theoretical interaction potential, dipole moment, and collision-induced absorption spectra.

Coupled cluster quantum chemical calculations of the potential energy surface and the induced dipole surface are reported for the He-Ar van der Waals collisional complex. Spectroscopic parameters are derived from global analytical fits while an accurate value for the long-range dipole coefficient D7 is obtained by perturbation methods. Collision-induced absorption spectra are computed quantum mechanically and compared with existing measurements.

Infrared absorption by collisional H2-He complexes at temperatures up to 9000 K and frequencies from 0 to 20,000 cm(-1).

Quantum chemical methods have been used elsewhere to obtain the potential energy surface (PES) and the induced dipole surface (IDS) of H(2)-He collisional complexes at eight different H-H bond distances, fifteen atom-molecule separations, and 19 angular orientations each [X. Li, A. Mandal, E. Miliordos, and K. L. C. Hunt, J. Chem. Phys. 136, 044320 (2012)]. An atom-molecule state-to-state scattering formalism is employed, which couples the collisional molecular complex to the electromagnetic radiation field. In this way, we obtain theoretical collision-induced absorption (CIA) spectra of H(2)-He complexes for frequencies from 0 to 20,000 cm(-1) and temperatures up to 9000 K. The work is based on the fundamental theory and is motivated by current research of certain astronomical objects, such as cool white dwarf stars, cool main sequence stars, M dwarfs, exoplanets, so-called "first" stars. We compare our theoretical results to existing laboratory measurements of CIA spectra; very close agreement of theory and measurement is observed. We also discuss similar previous theoretical efforts.

Collision-induced absorption by H2 pairs: from hundreds to thousands of kelvin.

An interaction-induced dipole surface (IDS) and a potential energy surface (PES) of collisionally interacting molecular hydrogen pairs H(2)-H(2) was recently obtained using quantum chemical methods (Li, X.; et al. Computational Methods in Science and Engineering, ICCMSE. AIP Conf. Proc. 2009, ; see also Li, X.; et al. Int. J. Spectrosc. 2010, ID 371201). The data account for substantial rotovibrational excitations of the H(2) molecules, as encountered at temperatures of thousands of kelvin (e.g., in the atmospheres of "cool" stars). In this work we use these results to compute the binary collision-induced absorption (CIA) spectra of dense hydrogen gas in the infrared at temperatures up to several thousand kelvin. The principal interest of the work is in the spectra at such higher temperatures, but we also compare our computations with existing laboratory measurements of CIA spectra of dense hydrogen gas and find agreement.

Collision-induced absorption at wavelengths near 5 microm by dense hydrogen gas.

Based on a recent ab initio interaction-induced dipole surface of collisionally interacting molecular hydrogen pairs H(2)-H(2), we compute the binary absorption coefficients at wavelengths near 5 microm at temperatures of 77.5 and 297 K for comparison with existing laboratory measurements. We observe satisfactory agreement of the measurements with our calculations, thereby concluding an earlier study [Gustafsson et al., J. Chem. Phys. 119, 12264 (2003)], which was based on an ab initio interaction-induced dipole surface that was inadequate for the 5 microm band.

Roto-translational Raman spectra of pairs of hydrogen molecules from first principles.

We calculate the collision-induced, roto-translational, polarized, and depolarized Raman spectra of pairs of H(2) molecules. The Schrodinger equation of H(2)-H(2) scattering in the presence of a weak radiation field is integrated in the close-coupled scheme. This permits the accounting for the anisotropy of the intermolecular potential energy surface and thereby it includes mixing of polarizability components. The static polarizability invariants, trace and anisotropy, of two interacting H(2) molecules were obtained elsewhere [Li et al., J. Chem. Phys. 126, 214302 (2007)] from first principles. Here we report the associated spherical tensor components which, along with the potential surface, are input in the calculation of the supramolecular Raman spectra. Special attention is paid to the interferences in the wings of the rotational S(0)(0) and S(0)(1) lines of the H(2) molecule. The calculated Raman pair spectra show reasonable consistency with existing measurements of the polarized and depolarized Raman spectra of pairs of H(2) molecules.

Infrared absorption by collisional CH4+X pairs, with X=He, H2, or N2.

Existing measurements of the collision-induced rototranslational absorption spectra of gaseous mixtures of methane with helium, hydrogen, or nitrogen are compared to theoretical calculations, based on refined multipole-induced and dispersion force-induced dipole moments of the interacting molecular pairs CH4-He, CH4-H2, and CH4-N2. In each case the measured absorption exceeds the calculations substantially at most frequencies. We present the excess absorption spectra, that is the difference of the measured and the calculated profiles, of these supramolecular CH4-X systems at various gas temperatures. The excess absorption spectra of CH4-X pairs differ significantly for each choice of the collision partner X, but show common features (spectral intensities and shape) at frequencies from roughly 200 to 500 cm(-1). These excess spectra seem to defy modeling in terms of ad hoc exchange force-induced dipole components attempted earlier. We suggest that besides the dipole components induced by polarization in the electric molecular multipole fields and their gradients, and by exchange and dispersion forces, other dipole induction mechanisms exist in CH4-X complexes that presumably are related to collisional distortion of the CH4 molecular frame.

Far-infrared absorption by collisionally interacting nitrogen and methane molecules.

Quantum line shape calculations of the rototranslational enhancement spectra of nitrogen-methane gaseous mixtures are reported. The calculations are based on a recent theoretical dipole function for interacting N(2) and CH(4) molecules, which accounts for the long-range induction mechanisms: multipolar inductions and dispersion force-induced dipoles. Multipolar induction alone was often found to approximate the actual dipole surfaces of pairs of interacting linear molecules reasonably well. However, in the case of the N(2)-CH(4) pair, the absorption spectra calculated with such a dipole function still show a substantial intensity defect at the high frequencies (>250 cm(-1)) when compared to existing measurements at temperatures from 126 to 297 K, much as was previously reported.

Microwave emission of sonoluminescing bubbles.

Kordomenos et al. have attempted to measure single bubble sonoluminescence (SBSL) emission in the microwave window of water in a band of frequencies ranging from 1.65 GHz to 2.35 GHz [Phys. Rev. E 59, 1781 (1999)]. The sensitivity of the experiment was such that signals greater than 1 nW would have been detected. We show here that this upper bound is compatible with the radiation processes that we think generate significant emission at optical frequencies, electron-neutral and electron-ion bremsstrahlung. In fact, we argue that, almost independently of the specific assumptions concerning the hydrodynamics or the nature of the radiative processes, SBSL intensities exceeding that upper bound can hardly be expected.

Light emission of sonoluminescent bubbles containing a rare gas and water vapor.

We present numerical simulations of sonoluminescent rare-gas bubbles in water, which account for (i) time variations of the water vapor content, (ii) chemical reactions, and (iii) the ionization of the rare gas and the H2O dissociation products. Peak temperatures exceed 10 000 K at densities of a few hundred amagat ( approximately 10(28) particles per m(3)). The gas mixture in the bubble is weakly ionized. Our model accounts for the light emission by electron-atom, electron-ion, and ion-atom bremsstrahlung, recombination radiation, and radiative attachment of electrons to hydrogen and oxygen atoms, which are all more or less important for single bubble sonoluminescence. Spectral shapes, spectral intensities, and durations of the light pulses are computed for helium, argon, and xenon bubbles. We generally obtain good agreement with the observations for photon numbers and pulse durations. Some calculated spectral profiles agree, however, less well with observations, especially in the case of the low water temperature and for helium bubbles. We try to identify the reasons why computed and observed spectral profiles might discernibly differ when all other computed features considered here seem to be quite consistent with observations. We show that by allowing the bubble to heat somewhat nonisotropically, agreement between observed and computed spectral profiles may be obtained, even in the case of helium bubbles at freezing water temperatures. In this case, charge exchange radiation and related processes involving helium atoms and ions become important.

Electron-ion bremsstrahlung spectra calculations for sonoluminescence.

The bremsstrahlung spectra arising from electron-ion collisions are calculated for temperatures from 5000 K to 40 000 K and wavelengths from 100 nm to 1000 nm, for the ions He+, Ne+, Ar+, Kr+, Xe+, H+, and O+, using Hartree-Fock-Slater potentials. The spectral intensities are expressed in terms of Gaunt factors, the ratios of the present quantum computation and existing semiclassical results. For the heavy rare gas ions Gaunt factors of up to 3 are obtained at wavelengths of 200 nm. We use these results to improve our calculations of rare gas sonoluminescence spectra [Phys. Rev. E 65, 046309 (2002)] and find that the improved overall sonoluminescence spectra hardly differ from our earlier results which were based on the semiclassical treatment of the electron-ion bremsstrahlung contributions. We think that in the conventional single-bubble sonoluminescence studies electron-ion bremsstrahlung amounts to but a small percentage of the overall emission. We also estimate here the effects of shielding of the ions due to a finite Debye length. Unless the Debye length is smaller than about 50 bohr, no significant influence of Debye shielding is discernible.