0000000000115960
AUTHOR
Grégoire Guillon
First-Principles Computed Rate Constant for the O + O 2 Isotopic Exchange Reaction Now Matches Experiment
We show, by performing exact time-independent quantum molecular scattering calculations, that the quality of the ground electronic state global potential energy surface appears to be of utmost importance in accurately obtaining even as strongly averaged quantities as kinetic rate constants. The oxygen isotope exchange reaction, 18O + 32O2, motivated by the understanding of a complex long-standing problem of isotopic ozone anomalies in the stratosphere and laboratory experiments, is explored in this context. The thermal rate constant for this key reaction is now in quantitative agreement with all experimental data available to date. A significant recent progress at the frontier of three rese…
Dependence on collision energy of the stereodynamical properties of the 18O + 32O2 exchange reaction
We report a quantum stereodynamical study of the 18O + 16O16O(v = 0, j = 1) → 18O16O(v′ = 0, j′) + 16O oxygen exchange reaction at four different collision energies. We calculated the polarisation ...
Direct time delay computation applied to the O + O2 exchange reaction at low energy: Lifetime spectrum of O3* species
We report full quantum dynamical calculations for lifetimes of scattering resonances, among which are true metastable states, of the intermediate heavy ozone complex 50O3* of the 18O + 16O16O reaction, for any value of the total angular momentum quantum number J. We show that computations for nonzero values of J are mandatory in order to properly analyze resonances and time delays, with a view to establish a somewhat comprehensive eigenlife spectrum of the complex O3*. Calculations have been performed in a given low to moderate energy range, including the interval between zero-point energies (ZPEs) of reagents and product species. Quasi-bound states tend to be more numerous, and eigenlifeti…
Huge Quantum Symmetry Effect in the O + O2 Exchange Reaction.
We report extensive, full quantum-mechanical calculations for the (16)O + (16)O(16)O → (16)O(16)O + (16)O collisions, for both inelastic and atom exchange processes, using a time-independent method based on hyperspherical coordinates. The rates obtained in the present study are much larger than the previously reported ones for this system. The discrepancy is attributed to a huge symmetry effect that was missing in the studies so far. This effect differs from the well-known isotope effect. Importance of this quantum effect is further confirmed by comparison with results for the (16)O + (18)O(18)O → (16)O(18)O + (18)O, exchange reaction.
Quantum stereodynamics of the 18O+16O16O→16O18O+16O exchange reaction at low collision energy
Abstract We present a quantum study of stereodynamics of the 18 O + 16 O 16 O ( v = 0 , j = 1 ) → 16 O 18 O ( v ′ = 0 , j ′ ) + 16 O exchange reaction at a collision energy E coll = 0.01 eV . Polarization moments of the reactants have been computed and stereodynamical portraits have been generated. The results show that the reactant preferred relative orientations are strongly dependent on the scattering angle and on the product rotational states.
Quantum dynamics of 16O in collision with ortho- and para-17O17O
Abstract We report full quantum dynamical observables, such as integral and differential cross sections and rate constants, for the 16 O + 17 O 17 O reactive collision process. We particularly emphasize the effect coming from the nonzero nuclear spin of 17 O, leading to two nuclear spin isomers of 34 O 2 , ortho- and para- 34 O 2 which can be studied independently and behave differently. A comparison with the 16 O + 18 O 18 O collision is given. We find that processes involving 17 O 17 O are always faster than with 18 O 18 O.
Quantum mechanical study of the high-temperature $\mathrm{H}^+ + \mathrm{HD} \to \mathrm{D}^+ + \mathrm{H}_2$ reaction for the primordial universe chemistry
We use the time-independent quantum-mechanical formulation of reactive collisions in order to investigate the state-to-state $\mathrm{H}^+ + \mathrm{HD} \to \mathrm{D}^+ + \mathrm{H}_2$ chemical reaction. We compute cross sections for collision energies up to 1.8 electron-volts and rate coefficients for temperatures up to 10000 kelvin. We consider HD in the lowest vibrational level $v=0$ and rotational levels $j=0$ to 4, and H$_2$ in vibrational levels $v'=0$ to 3 and rotational levels $j'=0$ to 9. For temperatures below 4000 kelvin, the rate coefficients strongly vary with the initial rotational level $j$, depending on whether the reaction is endothermic ($j\le 2$) or exothermic ($j\ge 3$)…
Quantum Dynamics of the 17O + 32O2 Collision Process
We report full quantum integral and differential cross sections and rate constants for the 17O + 32O2 reactive process. This constitutes the first quantum scattering study of the 17O16O16O system. We emphasize the comparison with the 18O + 32O2 collision in close connection to the mass-independent fractionation (hereafter referred to as MIF) puzzle for ozone in atmospheric chemistry. We find similar general trends in the cross sections and rate constants for both rare isotopes, but we note some singular behaviors peculiar to the use of 17O isotope, particularly at the lowest collision energies.
Quantum dynamics of 16O + 36O2 and 18O + 32O2 exchange reactions
We present quantum dynamical investigations of (16)O + (36)O2 and (18)O + (32)O2 exchange reactions using a time-independent quantum mechanical method and an accurate global potential energy surface of ozone [Dawes et al., J. Chem. Phys. 135, 081102 (2011)]. Initial state-selected integral cross sections, rate constants, and Boltzmann averaged thermal rate constants are obtained and compared with earlier experimental and theoretical results. The computed thermal rate constants for the oxygen exchange reactions exhibit a negative temperature dependence, as found experimentally. They are in better agreement with the experiments than the previous studies on the same reactions.
Temperature dependence of sodium and ionized calcium resonance lines perturbed by helium
International audience; Traces of heavy metals in cool DZ white dwarf stars may be attributed to the accretion of circumstellar dust thought to originate from tidal disruption of rocky parent bodies. Spectra of such stars therefore provide a unique opportunity to study the composition of extrasolar planetary systems. The determination of metal abundances from stellar spectra depends on stellar atmospheric parameters and an accurate prior knowledge of the collision broadening of the line profiles by the most common constituents of the stellar atmosphere. For this purpose, we present theoretical absorption spectra of Na and Ca+ broadened by He for the conditions prevailing in cool white dwarf…
Quantum Dynamics of the 18O + 36O2 Collision Process
We report full quantum cross sections and rate constants for the (18)O + (36)O2 → (36)O2 + (18)O collision process. This constitutes to the best of our knowledge the first dynamical study of the (18)O(18)O(18)O system, with three identical (18)O oxygen atoms. We emphasize the comparison with the (16)O + (32)O2 collision as this latter presents the exact same features as the one treated here, except the consistent change of mass for all three atoms. We find very similar behaviors in the cross sections, and we confirm that the rates are faster when three identical nuclei are involved. In particular, we cannot dynamically study this system with classical trajectory methods, and we have to incl…
Quantum mechanical study of the 16O + 18O18O → 16O18O + 18O exchange reaction: Integral cross sections and rate constants
The isotopic exchange reaction, 16O + 18O18O → 16O18O + 18O, involving excited ozone, O3*, as intermediate complex, was investigated by means of a time independent quantum mechanical approach using the TKTHS potential energy surface (PES) [V. G. Tyuterev et al., J. Chem. Phys. 139, 134307 (2013)] of ozone. State-to-state integral cross sections were calculated for collision energies lower than 0.4 eV. Then specific and thermal rate constants were computed between 10 K and 350 K using these cross sections. The full quantum thermal rate constant is found to be in better agreement with the most recent experimental data than with previous studies where other O3 PESs were employed, confirming th…
Differential cross sections and product ro-vibrational distributions for 16O+36O2 and 18O+32O2 exchange reactions
Abstract We report the rotational-state resolved integral cross sections and differential cross sections for 18O + 16O16O (v = 0, j = 1) → 18O16O ( v ′ = 0, j ′ ) + 16O and 16O + 18O18O (v = 0, j = 1) → 18O16O ( v ′ = 0, j ′ ) + 18O reactions obtained using time-independent quantum mechanical method on an ab initio potential energy surface of ozone [Dawes et al. J. Chem. Phys.135, 081102(2011)]. The results for both the reactions in the collision energy range of 0.001 – 0.1 eV are presented and discussed the isotopic effects found. The present results are compared with the earlier experimental and theoretical results reported in the literature.
Quantum dynamics of O17 in collision with ortho- and para- O17O17
We report full quantum scattering cross sections for the peculiar $^{17}\mathrm{O}+^{17}\mathrm{O}^{17}\mathrm{O}$ system, at relatively low collision energies. We consider different types of collision-induced transitions, as the indistinguishability of the three nuclei allows for the mixing of reactive, inelastic, and elastic processes. Furthermore, due to the nonzero nuclear spin of $^{17}\mathrm{O}$ and the existence of nuclear spin isomers ortho- and para-${\mathrm{O}}_{2}$, we pay particular attention to transitions between these two species, that is, the ortho-para conversion process. We find that the corresponding cross section has a magnitude comparable to that of the ${\mathrm{H}}^…
Differential Cross Sections and Product Rovibrational Distributions for (16)O + (32)O2 and (18)O + (36)O2 Collisions.
We report rotationally resolved opacity functions, product rotational distributions, and differential cross sections for the (16)O + (16)O(16)O (v = 0,j = 1) → (16)O(16)O (v' = 0,j') + (16)O and (18)O + (18)O(18)O (v = 0,j = 1) → (18)O(18)O (v' = 0,j') + (18)O collisions calculated by a time-independent quantum mechanical method employing one of the latest potential energy surface of ozone [ Dawes ; et al. J. Chem. Phys. 2013 , 139 , 201103 ]. The results obtained for both collisional systems in the energy range 0.001-0.2 eV are examined, and interesting mass scaling effects have been discovered. The shapes of product angular distributions suggest a transition from an indirect to a direct s…
Extension of the Launay Quantum Reactive Scattering Code and Direct Computation of Time Delays.
Scattering computations, particularly within the realm of molecular physics, have seen an increase in study since the development of powerful quantum methods. These dynamical processes can be analyzed via (among other quantities) the duration of the collision process and the lifetime of the intermediate complex. We use the Smith matrix Q = -iℏS†dS/dE calculated from the scattering matrix S and its derivative with respect to the total energy. Its real part contains the state-to-state time delays, and its eigenvalues give the lifetimes of the metastable states [ Smith Phys. Rev. 1960 , 118 , 349 - 356 ]. We propose an extension of the Launay HYP3D code [ Launay and Le Dourneuf Chem. Phys. Let…
Quantum mechanical study of the high-temperature H+ + HD → D+ + H2 reaction for the primordial universe chemistry
ABSTRACT We use the time-independent quantum-mechanical formulation of reactive collisions in order to investigate the state-to-state H+ + HD → D+ + H2 chemical reaction. We compute cross-sections for collision energies up to 1.8 eV and rate coefficients for temperatures up to 10 000 K. We consider HD in the lowest vibrational level v = 0 and rotational levels j = 0–6, and H2 in vibrational levels v′ = 0–3 and rotational levels j′ = 0–9. For temperatures below 4000 K, the rate coefficients strongly vary with the initial rotational level j, depending on whether the reaction is endothermic (j ≤ 2) or exothermic (j ≥ 3). The reaction is also found less and less probable as the final vibrationa…
Theoretical profiles of the Mg + resonance lines perturbed by collisions with He
International audience; The effects of collision broadening by He are central to understanding the opacity of cool stellar atmospheres. Aims. DZ white dwarfs show metal lines which are, in many cases, believed to come from some rocky material, a remnant of a former exoplanetary system. The analysis of the Mg + resonance lines is a valuable method to determine the chemical abundances in these systems. Methods. Unified profiles of the strongest of the UV lines of Mg + have been calculated in the semi-classical approach using very recent ab initio potential energies. Results. We present the first theoretical line profile calculations of the resonance lines of Mg + that have been perturbed by h…
H-He collision-induced satellite in the Lyman alpha profile of DBA white dwarf stars
The spectra of helium-dominated white dwarf stars with hydrogen in their atmosphere present a distinctive broad feature centered around 1160~\AA\/ in the blue wing of the Lyman-$\alpha$ line. It is extremely apparent in WD 1425+540 recently observed with HST COS. With new theoretical line profiles based on ab initio atomic interaction potentials we show that this feature is a signature of a collision-induced satellite due to an asymptotically forbidden transition. This quasi-molecular spectral satellite is crucial to understanding the asymmetrical shape of Lyman-$\alpha$ seen in this and other white dwarf spectra. Our previous work predicting this absorption feature was limited by molecular…