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Laboratory measurements of the far infrared absorption of H2 and of mixtures of H2 with CH4 and He are presented, and fits to the pure H2 spectra with a semiempirical line shape are described. Such results are needed in analyzing the thermal emission from the atmospheres of the outer planets.
Relative total scattering cross sections for normal H2 + normal H2, para-H2 + para-H2, normal D2 + normal D2, ortho-D2 + ortho-D2, and HD + HD were measured at energy below 10 meV by colliding particles from two inclined nozzle beams. Cross sections for the H2 + H2 pairs were measured over a relative velocity range of 200-1450 m/s; the normal H2 + normal H2 results suggest a l = 3 orbiting resonance near 375 m/s while the para-H2 + para-H2 results have a l = 4 orbiting resonance near 585 m/s. This latter resonance has a peak energy of 1.79 meV and a FWHM of 1.05 meV. The D2 + D2 cross sections were measured over the velocity range of 190 to 1000 m/s and a minimum between the l = 4 and l = 5 orbiting resonances was observed. Some preliminary measurements on HD + HD over the range of 250-1250 m/s indicate a possible l = 4 orbiting resonance near 300 m/s. The experimental work compares favorably to cross sections calculated from a theoretical potential.
Rotational cross sections for transitions in the H2-H2 system have been calculated for energies up to about 2.0 eV and for rotor levels up to j = 11 in the effective potential approximation. The cases of para H2-para H2, ortho H2-ortho H2 and ortho H2-para H2 are considered. Correlations and trends in the cross sections have been examined, and it is shown that the high-energy collisions are dominated by coupling effects. The results of this analysis also suggest that the collision process may be profitably viewed as a diffusion of probability among the levels.
Semiempirical electric dipole moment and derivative in molecular-molecular and molecular-atomic collisions of hydrogen
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A laser fluorescence technique is used for the direct observation of the vibrational relaxation of H2 in the presence of D2 and HCl. The technique used is much simpler than the Raman absorption laser-schlieren method and has the advantage that the direct observation of changes in the vibrational energy of H2 permits the study of V-V relaxation processes in mixtures of H2 with other gases. The rapid V-V transfer between HF and H2 is used to permit the selective vibrational excitation of H2 by trace amounts of HF excited by laser absorption. The subsequent relaxation of vibrational energy from the coupled HF and H2 molecules is monitored by the laser induced fluorescence of HF.
High-resolution spectra of oxygen-enriched samples of water vapor were recorded with a Fourier-transform spectrometer covering transitions in the (010)-(000) bands. The measured line frequencies were used along with measurements taken from studies at microwave and far-infrared frequencies to obtain rotational energy levels in the (000) and (010) states of H2 O-17 and H2 O-18. Measurements of the line strengths were fitted to a model in which as many as 18 transition moment parameters were determined. The results produced computed line-strength values that are in excellent agreement with the 623 H2 O-17 experimental transition strengths and 696 H2 O-18 values. These results provide a more accurate representation of the line positions and strengths for the (010)-(000) bands of H2 O-17 and H2 O-18 than those previously available.
Vibrational absorption by H2 and CO has been searched for toward infrared sources embedded in molecular clouds. H2 was detected toward NGC 2024 IRS 2 and possibly toward NGC 2264 (GL 989). CO was detected toward both sources. The results are consistent with the H2 ortho:para ratio being equilibrated at the cloud temperature. Toward NGC 2024, H2:CO = (3700(sub -2600)(sup +3100)) (2 sigma limits), and toward NGC 2264, H2:CO less than 6000. Approximately one-third of all carbon is in gas-phase CO.
The computation of the far-infrared, rototranslational (RT) collision-induced absorption (CIA) spectra of H2-H2 pairs is presented at temperatures from 600 to 7000 K for the first time. Theoretical results are based on the quantum mechanical and semiclassical, three lowest translational spectral moments obtained for H2 pairs. The effective, isotropic H2-H2 interaction potential, suitable for the high-temperature computations, and the ab initio induced dipoles, have been used as input. Special effort has been made to account for the rotational and vibrational states dependence of the dipoles, since it was found to be relevant at the high temperatures employed. The computations of the entire RT band account for all populated vibrational states of hydrogen molecule and include vibrational transitions v tends towards v-prime = v, with v = 0, 1, 2 and 3. The described method makes use of the adequately selected model line shapes with the temperature-dependent parameters. The presented model is useful for the 'model atmospheres' of zero- and low-metallicity, cool and dense stellar atmospheres, where CIA is known to be imporatnt.
Collision-induced absorption in the translation-rotation band of H2 and H2-He mixtures has been measured from 20 to 900 kaysers at 77.4, 195, and 292 K. To establish the accuracy of the results, various sources of error are investigated. The zeroth and first spectral moments are evaluated from experiment and theory for H2 at the various temperatures. To obtain theoretical moments consistent with the experimental values, the quantum pair-distribution function must be used. The major portion of the experimental moments can be accounted for by quadrupole-induced dipoles in H2 pairs. The remaining portion is attributable to an anisotropic overlap interaction, although its magnitude depends on the value of the molecular parameters required to calculate the quadrupole contribution.
A new global potential energy hypersurface for H2 + H2 is constructed and quasiclassical trajectory calculations performed using the resonance complex theory and energy transfer mechanism to estimate the rate of three body recombination over the temperature range 100 to 5000 K. The new potential is a faithful representation of ab initio electron structure calculations, is unchanged under the operation of exchanging H atoms, and reproduces the accurate H3 potential as one H atom is pulled away. Included in the fitting procedure are geometries expected to be important when one H2 is near or above the dissociation limit. The dynamics calculations explicitly include the motion of all four atoms and are performed efficiently using a vectorized variable-stepsize integrator. The predicted rate constants are approximately a factor of two smaller than experimental estimates over a broad temperature range.
A new global potential energy hypersurface for H2 + H2 is constructed and quasiclassical trajectory calculations performed using the resonance complex theory and energy transfer mechanism to estimate the rate of three body recombination over the temperature range 100 to 5000 K. The new potential is a faithful representation of ab initio electron structure calculations, is unchanged under the operation of exchanging H atoms, and reproduces the accurate H3 potential as one H atom is pulled away. Included in the fitting procedure are geometries expected to be important when one H2 is near or above the dissociation limit. The dynamics calculations explicitly include the motion of all four atoms and are performed efficiently using a vectorized variable-stepsize integrator. The predicted rate constants are approximately a factor of two smaller than experimental estimates over a broad temperature range.
The main objective of the proposal was to model the collision induced, second overtone band of gaseous hydrogen at low temperatures. The aim of this work is to assist planetary scientists in their investigation of planetary atmospheres, mainly those of Uranus and Neptune. The recently completed extended database of collision induced dipole moments of hydrogen pairs allowed us, for the first time, to obtain dipole moment matrix elements responsible for the roto-vibrational collision induced absorption spectra of H2-H2 in the second overtone band. Despite our numerous attempts to publish those data, the enormous volume of the database did not allow us to do this. Instead, we deposited the data on a www site. The final part of this work has been partially supported by NASA, Division for Planetary Atmospheres. In order to use our new data for modelling purpose, we first needed to test how well we can reproduce the existing experimental data from theory, when using our new input data. Two papers resulted from this work. The obtained agreement between theoretical results and the measurements appeared to be within 10-30%. The obviously poorer agreement than observed for the first H2 overtone, the fundamental, and the rototranslational bands can be attributed to the fact that dipole moments responsible for the second overtone are much weaker, therefore susceptible to larger numerical uncertainties. At the same time, the intensity of the second overtone band is much weaker and therefore it is much harder to be measured accurately in the laboratory. We need to point out that until now, no dependable model of the 2nd overtone band was available for modelling of the planetary atmospheres. The only one, often referred to in previous works on Uranian and Neptune's atmospheres, uses only one lineshape, with one (or two) parameter(s) deduced at the effective temperature of Uranus (by fitting the planetary observation). After that, the parameter(s) was(were) made temperature dependent according to some very simple relation. Summarizing, no reliable temperature-dependent model has been available yet. Our approach was a bit different from similar attempts done earlier, on account of the poorer agreement of theory with experiment. We needed to resort to some semi-empirical procedure. While we were in a favourable position to be able to rely on the physical input data, these, apparently, did not supply the most dependable predictions (simply because the results did not agree well enough with experimental data). On the other hand, the relative deviations between the theory and experiment were comparable at 77 and at 298 K. That fact indicated that theory is capable of predicting the temperature dependence of the absorption spectra well. We have thus chosen the "middle way". We have fitted the existing measurements with many 3- parameter lineshapes, in order to achieve the closest fit.
Isothermal radiative intensity calculations for 100% H2 and 87% H2-13% He are presented for temperatures of 10,000-25,000 K, density ratios of .0001 to .1, and path lengths of 1.0-30.0 cm. The actual spectral details of the absorption coefficient were computed for 16,000 points from 240 to 30,000 A by summing the various line and continuum radiative processes at each point. This method should result in a very accurate calculation of radiative emission, including an accurate accounting for reabsorption due to overlapping lines.
The paper reports extensive quantum mechanical calculations of the product vibrational branching ratios in the reaction H + p-H2 yields o-H2 + H. The calculations involve total angular momentum up to 2 and excited as well as ground initial rotational states, and they are completely converged with up to 513 channels in individual total angular momentum/parity blocks. Comparisons are made with recent experiments by Nieh and Valentini.
A diabatic representation is presented of the coupled potential-energy surfaces for Na(3p P-2) + H2 yields Na (3s S-2) + H2 or NaH + H. The representation is designed to yield, upon diagonalization, realistic values for the two lowest energy adiabatic states at both asymptotes of the chemical reaction as well as near the conical intersection in the three-body interaction region. It is economical to evaluate and portable. It is suitable for dynamics calculations on both the quenching process and the electronically nonadiabatic chemical reaction.
The potential energy surface (PES) for the CH3OH system has been characterized for the (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO product channels using complete-active-space self-consistent-field (CASSCF) gradient calculations to determine the stationary point geometries and frequencies followed by CASSCF/internally contracted configuration-interaction (CCI) calculations to refine the energetics. The (1)CH2 + H2O channel is found to have no barrier. The long range interaction is dominated by the dipole-dipole term, which orients the respective dipole moments parallel to each other but pointing in opposite directions. At shorter separations there is a dative bond structure in which a water lone pair donates into the empty a" orbital of CH2. Subsequent insertion of CH2 into an OH bond of water have barriers located at -5.2 kcal/mol and 1.7 kcal/mol, respectively, with respect to CH3 + OH. From comparison of the computed energetics of the reactants and products to known thermochemical data it is estimated that the computed PES is accurate to plus or minus 2 kcal/mol.
The potential energy surface (PES) for the CH3OH system has been characterized for the (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO product channels using complete-active-space self-consistent-field (CASSCF) gradient calculations to determine the stationary point geometries and frequencies followed by CASSCF/internally contracted configuration-interaction (CCI) calculations to refine the energetics. The (1)CH2 + H2O channel is found to have no barrier. The long range interaction is dominated by the dipole-dipole term, which orients the respective dipole moments parallel to each other but pointing in opposite directions. At shorter separations there is a dative bond structure in which a water lone pair donates into the empty 'a' orbital of CH2. Subsequent insertion of CH2 into an OH bond of water have barriers located at -5.2 kcal/mol and 1.7 kcal/mol, respectively, with respect to CH3 + OH. From comparison of the computed energetics of the reactants and products to known thermochemical data it is estimated that the computed PES is accurate to plus or minus 2 kcal/mol.