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Register a new userReaction Rates and Kinetic Isotope Effects of H$_2$ + OH $rightarrow$ H$_2$O + H
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We calculated reaction rate constants including atom tunneling of the reaction of dihydrogen with the hydroxy radical down to a temperature of 50 K. Instanton theory and canonical variational theory with microcanonical optimized multidimensional tunneling (CVT/$mu$OMT) were applied using a fitted potential energy surface [J. Chem. Phys. 138, 154301 (2013)]. All possible protium/deuterium isotopologues were considered. Atom tunneling increases at about 250 K (200 K for deuterium transfer). Even at 50 K the rate constants of all isotopologues remain in the interval $ 4 cdot 10^{-20}$ to $4 cdot 10^{-17}$ cm$^3$ s$^{-1}$ , demonstrating that even deuterat
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The non-adiabatic quantum dynamics of the H+H$_2^+$ $rightarrow$ H$_2$+ H$^+$ charge transfer reactions, and some isotopic variants, is studied with an accurate wave packet method. A recently developed $3times$3 diabatic potential model is used, which is based on very accurate {it ab initio} calculations and includes the long-range interactions for ground and excited states. It is found that for initial H$_2^+$(v=0), the quasi-degenerate H$_2$(v=4) non-reactive charge transfer product is enhanced, producing an increase of the reaction probability and cross section. It becomes the dominant channel from collision energies above 0.2 eV, producing a ratio, between v=4 and the rest of vs, that increases up to 1 eV. H+H$_2^+$ $rightarrow$ H$_2^+$+ H exchange reaction channel is nearly negligible, while the reactive and non-reactive charge transfer reaction channels are of the same order, except that corresponding to H$_2$(v=4), and the two charge transfer processes compete below 0.2 eV. This enhancement is expected to play an important vibrational and isotopic effect that need to be evaluated. For the three proton case, the problem of the permutation symmetry is discussed when using reactant Jacobi coordinates.
Deuterated molecules are important chemical tracers of prestellar and protostellar cores. Up to now, the titular reaction has been assumed to contribute to the generation of these deuterated molecules. We have measured the merged-beams rate coefficient for this reaction as function of the relative collision energy in the range of about 10 meV to 10 eV. By varying the internal temperature of the reacting H$_3^+$ molecules, we found indications for the existence of a reaction barrier. We have performed detailed theoretical calculations for the zero-point-corrected energy profile of the reaction and determined a new value for the barrier height of $approx$ 68 meV. Furthermore, we have calculated the tunneling probability through the barrier. Our experimental and theoretical results show that the reaction is essentially closed at astrochemically relevant temperatures. We derive a thermal rate coefficient of $<1times 10^{-12}$ cm$^3$ s$^{-1}$ for temperatures below 75 K with tunneling effects included and below 155 K without tunneling.
Supersonic turbulence results in strong density fluctuations in the interstellar medium (ISM), which have a profound effect on the chemical structure. Particularly useful probes of the diffuse ISM are the ArH$^+$, OH$^+$, H$_2$O$^+$ molecular ions, which are highly sensitive to fluctuations in the density and the H$_2$ abundance. We use isothermal magnetohydrodynamic (MHD) simulations of various sonic Mach numbers, $mathcal{M}_s$, and density decorrelation scales, $y_{rm dec}$, to model the turbulent density field. We post-process the simulations with chemical models and obtain the probability density functions (PDFs) for the H$_2$, ArH$^+$, OH$^+$ and H$_2$O$^+$ abundances. We find that the PDF dispersions increases with increasing $mathcal{M}_s$ and $y_{rm dec}$, as the magnitude of the density fluctuations increases, and as they become more coherent. Turbulence also affects the median abundances: when $mathcal{M}_s$ and $y_{rm dec}$ are high, low-density regions with low H$_2$ abundance become prevalent, resulting in an enhancement of ArH$^+$ compared to OH$^+$ and H$_2$O$^+$. We compare our models with Herschel observations. The large scatter in the observed abundances, as well as the high observed ArH$^+$/OH$^+$ and ArH$^+$/H$_2$O$^+$ ratios are naturally reproduced by our supersonic $(mathcal{M}_s=4.5)$, large decorrelation scale $(y_{rm dec}=0.8)$ model, supporting a scenario of a large-scale turbulence driving. The abundances also depend on the UV intensity, CR ionization rate, and the cloud column density, and the observed scatter may be influenced by fluctuations in these parameters.
The $1 ^3Sigma_u^- leftarrow X^3Sigma_g^-$ transition of linear HC$_5$H (A) has been observed in a neon matrix and gas phase. The assignment is based on mass-selective experiments, extrapolation of previous results of the longer HC$_{2n+1}$H homologues, and density functional and multi-state CASPT2 theoretical methods. Another band system starting at 303 nm in neon is assigned as the $1 ^1 A_1 leftarrow X ^1 A_1$ transition of the cumulene carbene pentatetraenylidene H$_2$C$_5$ (B).
This work presents swarm parameters of electrons (the bulk drift velocity, the bulk longitudinal component of the diffusion tensor, and the effective ionization frequency) in C$_2$H$_n$, with $n =$ 2, 4 and 6, measured in a scanning drift tube apparatus under time-of-flight conditions over a wide range of the reduced electric field, 1 Td $leq,E/N,leq$ 1790 Td (1 Td = $10^{-21}$ Vm$^2$). The effective steady-state Townsend ionization coefficient is also derived from the experimental data. A kinetic simulation of the experimental drift cell allows estimating the uncertainties introduced in the data acquisition procedure and provides a correction factor to each of the measured swarm parameters. These parameters are compared to results of previous experimental studies, as well as to results of various kinetic swarm calculations: solutions of the electron Boltzmann equation under different approximations (multiterm and density gradient expansions) and Monte Carlo simulations. The experimental data are consistent with most of the swarm parameters obtained in earlier studies. In the case of C$_2$H$_2$, the swarm calculations show that the thermally excited vibrational population should not be neglected, in particular, in the fitting of cross sections to swarm results.
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