Deuterium fractionation on interstellar grains studied with modified rate equations and a Monte Carlo approach

The formation of singly and doubly deuterated isotopomers of formaldehyde and of singly, doubly, and multiply deuterated isotopomers of methanol on interstellar grain surfaces has been studied with a semi-empirical modified rate approach and a Monte Carlo method in the temperature range 10-20 K. Agreement between the results of the two methods is satisfactory for all major and many minor species throughout this range. If gas-phase fractionation can produce a high abundance of atomic deuterium, which then accretes onto grain surfaces, diffusive surface chemistry can produce large abundances of deuterated species, especially at low temperatures and high gas densities. Warming temperatures will then permit these surface species to evaporate into the gas, where they will remain abundant for a considerable period. We calculate that the doubly deuterated molecules CHD2OH and CH2DOD are particularly abundant and should be searched for in the gas phase of protostellar sources. For example, at 10 K and high density, these species can achieve up to 10-20% of the abundance of methanol.Comment: 27 pages, 3 figures, Planetary and Space Science, in pres

Several Levels of Theory for Description of Isotope Effects in Ozone: Symmetry Effect and Mass Effect

The essential components of theory for the description of isotope effects in recombination reaction that forms ozone are presented, including the introduction of three reaction pathways for symmetric and asymmetric isotopomers, a brief review of relevant experimental data for singly- and doubly substituted isotopologues, the definitions of ζ-effect and η-effect, and the introduction of isotopic enrichment δ. Two levels of theory are developed to elucidate the role of molecular symmetry, atomic masses, vibrational zero-point energies, and rotational excitations in the recombination process. The issue of symmetry is not trivial, since the important factors, such as 1/2 and 2, appear in seven different places in the formalism. It is demonstrated that if all these effects are taken into account properly, then no anomalous isotope effects emerge. At the next level of theory, a model is considered in which one scattering resonance (sitting right at the top of centrifugal barrier) is introduced per ro-vibrational channel. It is found that this approach is equivalent to statistical treatment with partition functions at the transition state. Accurate calculations using hyper-spherical coordinates show that no isotope effects come from difference in the number of states. In contrast, differences in vibrational and rotational energies lead to significant isotope effects. However, those effects appear to be local, found for the rather extreme values of rotational quantum numbers. They largely cancel when rate coefficients are computed for the thermal distribution of rotational excitations. Although large isotope effects (observed in experiments) are not reproduced here, this level of theory can be used as a foundation for more detailed computational treatment, with accurate information about resonance energies and lifetimes computed and included

On Stabilization of Scattering Resonances in Recombination Reaction that Forms Ozone

Calculations of energy transfer in the recombination reaction that forms ozone are carried out within the framework of the mixed quantum/classical theory and using the dimensionally reduced 2D-model of ozone molecule, with bending motion neglected. Recombination rate coefficients are obtained at room temperature for symmetric and asymmetric isotopomers of singly and doubly substituted isotopologues. The processes of resonance formation, spontaneous decay, collisional dissociation, and stabilization by bath gas (Ar) are all characterized and taken into account within the steady-state approximation for kinetics. The focus is on stabilization step, where the mysterious isotopic η-effect was thought to originate from. Our results indicate no difference in cross sections for stabilization of scattering resonances in symmetric and asymmetric isotopomers. As practical results, the general and simple analytic models for stabilization and dissociation cross sections are presented, which can be applied to resonances in any ozone molecule, symmetric or asymmetric, singly or doubly substituted. Present calculations show some isotope effect that looks similar to the experimentally observed η-effect, and the origin of this phenomenon is in the rates of formation/decay of scattering resonances, determined by their widths, that are somewhat larger in asymmetric isotopomers than in their symmetric analogues. However, the approximate two-dimensional model used here is insufficient for consistent and reliable description of all features of the isotopic effect in ozone. Calculations using an accurate 3D model are still needed

On the electron-induced isotope fractionation in low temperature ³²O₂/³⁶O₂ ices—ozone as a case study

The formation of six ozone isotopomers and isotopologues, 16O16O16O, 18O18O18O, 16O16O18O, 18O18O16O, 16O18O16O, and 18O16O18O, has been studied in electron-irradiated solid oxygen 16O2 and 18O2 (1 : 1) ices at 11 K. Significant isotope effects were found to exist which involved enrichment of 18O-bearing ozone molecules. The heavy 18O18O18O species is formed with a factor of about six higher than the corresponding 16O16O16O isotopologue. Likewise, the heavy 18O18O16O species is formed with abundances of a factor of three higher than the lighter 16O16O18O counterpart. No isotope effect was observed in the production of 16O18O16O versus 18O16O18O. Such studies on the formation of distinct ozone isotopomers and isotopologues involving non-thermal, non-equilibrium chemistry by irradiation of oxygen ices with high energy electrons, as present in the magnetosphere of the giant planets Jupiter and Saturn, may suggest that similar mechanisms may contribute to the 18O enrichment on the icy satellites of Jupiter and Saturn such as Ganymede, Rhea, and Dione. In such a Solar System environment, energetic particles from the magnetospheres of the giant planets may induce non-equilibrium reactions of suprathermal and/or electronically excited atoms under conditions, which are quite distinct from isotopic enrichments found in classical, thermal gas phase reactions

Positionally dependent ^(15)N fraction factors in the UV photolysis of N_2O determined by high resolution FTIR spectroscopy

Positionally dependent fractionation factors for the photolysis of isotopomers of N_2O in natural abundance have been determined by high resolution FTIR spectroscopy at three photolysis wavelengths. Fractionation factors show clear 15N position and photolysis wavelength dependence and are in qualitative agreement with theoretical models but are twice as large. The fractionation factors increase with photolysis wavelength from 193 to 211 nm, with the fractionation factors at 207.6 nm for ^(14)N^(15)N^916)O, ^(15)N^(14)N^(16)O and ^(14)N^(14)N^(18)O equal to −66.5±5‰,−27.1±6‰ and −49±10‰, respectively

Isotopomer Fractionation in the UV Photolysis of N_2O: 3. 3D Ab Initio Surfaces and Anharmonic Effects

The wavelength-dependent isotopic fractionation of N_2O is calculated, extending our previous work, Parts 1 and 2, in several aspects: (1) the fully three-dimensional ab initio electronic potential and transition dipole moment surfaces of S. Nanbu and M. S. Johnson (J. Chem. Phys. A 2004, 108, 8905) are used to calculate the absorption cross sections, instead of a 2D surface and (2) the vibrational frequencies and wave functions with anharmonicity correction are used for the ground electronic state. The results for the absorption spectrum and for the isotopic fractionation of the different isotopomers are discussed. One difference between experiments measuring the absorption coefficient (von Hessberg et al. Atmos. Chem. Phys. 2004, 4, 1237) and the others that measure instead the photodissociation is also discussed. Experiments on the quantum yield for wavelengths longer than 200 nm (>50000 cm^(−1)) would be helpful in treating the observed difference

Three-isotope plot of fractionation in photolysis: A perturbation theoretical expression

The slope of the three-isotope plot for the isotopomer fractionation by direct or nearly direct photodissociation is obtained using a perturbation theoretical analysis. This result, correct to first order in the mass difference, is the same as that for equilibrium chemical exchange reactions, a similarity unexpected a priori. A comparison is made with computational results for N2O photodissociation. This theoretical slope for mass-dependent photolytic fractionation can be used to analyze the data for isotopic anomalies in spin-allowed photodissociation reactions. Earlier work on chemical equilibria is extended by avoiding a high-temperature approximation

First detection of triply-deuterated methanol

We report the first detection of triply-deuterated methanol, with 12 observed transitions, towards the low-mass protostar IRAS 16293-2422, as well as multifrequency observations of 13CH3OH, used to derive the column density of the main isotopomer CH3OH. The derived fractionation ratio [CD3OH]/[CH3OH] averaged on a 10'' beam is 1.4%. Together with previous CH2DOH and CHD2OH observations, the present CD3OH observations are consistent with a formation of methanol on grain surfaces, if the atomic D/H ratio is 0.1 to 0.3 in the accreting gas. Such a high atomic ratio can be reached in the frame of gas-phase chemical models including all deuterated isotopomers of H3+.Comment: Accepted by A&