Communication: An accurate global potential energy surface for the ground electronic state of ozone

Dawes, Richard; Lolur, Phalgun; Li, Anyang; Jiang, Bin; Guo, Hua

doi:10.1063/1.4837175

Cited by 110 publications

(138 citation statements)

References 40 publications

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“…[46][47][48] It has a flat shoulder in the channels region, instead of a reef. This surface already allowed to improve temperature dependence of the atom-exchange rates in O 2 + O collisions [43][44][45] and may help to resolve some of the issues discussed above.…”

Section: Discussionmentioning

confidence: 99%

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On stabilization of scattering resonances in recombination reaction that forms ozone

Ivanov

Babikov

2016

The Journal of Chemical Physics

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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. Published by AIP Publishing. [http://dx

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Section: Discussionmentioning

confidence: 99%

“…However, the present two-dimensional model is too rough and incapable of describing consistently all the features of the isotopic effects in ozone. Calculations using an accurate 3D model, 40 and a new PES of Dawes, [46][47][48] are ongoing and will be reported elsewhere.…”

Section: Discussionmentioning

confidence: 99%

On stabilization of scattering resonances in recombination reaction that forms ozone

Ivanov

Babikov

2016

The Journal of Chemical Physics

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“…The description of the ground state dissociation path and the recovery of the experimental dissociation energy have proven particularly challenging and required extremely accurate wave functions. [22][23][24] Conversely, the theoretical approach has revealed certain features of the ground state potential energy surface that have posed a great challenge to experimentalists. Many high level ab initio calculations have established beyond any doubt that there exists a metastable ring structure of ozone with D 3h symmetry.…”

Section: Introductionmentioning

confidence: 99%

The transition from the open minimum to the ring minimum on the ground state and on the lowest excited state of like symmetry in ozone: A configuration interaction study

Theis

Ivanic

Windus

et al. 2016

The Journal of Chemical Physics

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The metastable ring structure of the ozone 1 1 A 1 ground state, which theoretical calculations have shown to exist, has so far eluded experimental detection. An accurate prediction for the energy difference between this isomer and the lower open structure is therefore of interest, as is a prediction for the isomerization barrier between them, which results from interactions between the lowest two 1 A 1 states. In the present work, valence correlated energies of the 1 1 A 1 state and the 2 1 A 1 state were calculated at the 1 1 A 1 open minimum, the 1 1 A 1 ring minimum, the transition state between these two minima, the minimum of the 2 1 A 1 state, and the conical intersection between the two states. The geometries were determined at the full-valence multi-configuration self-consistent-field level. Configuration interaction (CI) expansions up to quadruple excitations were calculated with triple-zeta atomic basis sets. The CI expansions based on eight different reference configuration spaces were explored. To obtain some of the quadruple excitation energies, the method of Correlation Energy Extrapolation by Intrinsic Scaling was generalized to the simultaneous extrapolation for two states. This extrapolation method was shown to be very accurate. On the other hand, none of the CI expansions were found to have converged to millihartree (mh) accuracy at the quadruple excitation level. The data suggest that convergence to mh accuracy is probably attained at the sextuple excitation level. On the 1 1 A 1 state, the present calculations yield the estimates of (ring minimum-open minimum) ∼45-50 mh and (transition state-open minimum) ∼85-90 mh. For the (2 1 A 1 -1 A 1 ) excitation energy, the estimate of ∼130-170 mh is found at the open minimum and 270-310 mh at the ring minimum. At the transition state, the difference (2 1 A 1 -1 A 1 ) is found to be between 1 and 10 mh. The geometry of the transition state on the 1 1 A 1 surface and that of the minimum on the 2 1 A 1 surface nearly coincide. More accurate predictions of the energy differences also require CI expansions to at least sextuple excitations with respect to the valence space. For every wave function considered, the omission of the correlations of the 2s oxygen orbitals, which is a widely used approximation, was found to cause errors of about ±10 mh with respect to the energy differences. C 2016 AIP Publishing LLC. [http://dx

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“…24 This PES for the O + O 2 system is characterized by a deep well corresponding to O 3 , with a submerged potential barrier ("reef") in the O + O 2 entrance/exit channel, now thought to be an artifact. [25][26][27] If the complex lived long enough, then the energy would be completely randomized among the degrees of freedom, and the products would be scattered into all spatial directions with equal probability, corresponding to a forward-backward symmetric c.m. angular distribution.…”

Section: Introductionmentioning

confidence: 99%

Dynamics of the O-Atom Exchange Reaction ¹⁶O(³P) + ¹⁸O¹⁸O(³Σ_g^–) → ¹⁶O¹⁸O(³Σ_g^–) + ¹⁸O(³P) at Hyperthermal Energies

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Communication: An accurate global potential energy surface for the ground electronic state of ozone

Cited by 110 publications

References 40 publications

On stabilization of scattering resonances in recombination reaction that forms ozone

On stabilization of scattering resonances in recombination reaction that forms ozone

The transition from the open minimum to the ring minimum on the ground state and on the lowest excited state of like symmetry in ozone: A configuration interaction study

Dynamics of the O-Atom Exchange Reaction ¹⁶O(³P) + ¹⁸O¹⁸O(³Σ_g^–) → ¹⁶O¹⁸O(³Σ_g^–) + ¹⁸O(³P) at Hyperthermal Energies

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Communication: An accurate global potential energy surface for the ground electronic state of ozone

Cited by 110 publications

References 40 publications

On stabilization of scattering resonances in recombination reaction that forms ozone

On stabilization of scattering resonances in recombination reaction that forms ozone

The transition from the open minimum to the ring minimum on the ground state and on the lowest excited state of like symmetry in ozone: A configuration interaction study

Dynamics of the O-Atom Exchange Reaction 16O(3P) + 18O18O(3Σg–) → 16O18O(3Σg–) + 18O(3P) at Hyperthermal Energies

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Dynamics of the O-Atom Exchange Reaction ¹⁶O(³P) + ¹⁸O¹⁸O(³Σ_g^–) → ¹⁶O¹⁸O(³Σ_g^–) + ¹⁸O(³P) at Hyperthermal Energies