Global permutationally invariant potential energy surface for ozone forming reaction

Abstract

We constructed new global potential energy surface for O + O 2 → O 3 reaction. It is based on high level electronic structure theory calculations and employs fitting by permutationally invariant polynomial functions. This method of surface construction takes full advantage of permutation symmetry of three O nuclei and allows reducing dramatically the number of ab initio data points needed for accurate surface representation. New potential energy surface offers dramatic improvement over older surface of ozone in terms of dissociation energy and behavior along the minimum energy path. It can be used to refine the existing theories of ozone formation.

Communication: Rigorous quantum dynamics of O + O2 exchange reactions on an ab initio potential energy surface substantiate the negative temperature dependence of rate coefficients

“…Electronic addresses: zsun@dicp.ac.cn; dawesr@mst.edu; and hguo@unm.edu nel of the O 3 PES, which has been found in most of previous ab initio calculations. [17][18][19][20] They showed that if the PES was adjusted to remove the "reef," interestingly, the calculated rate coefficients then took on a negative temperature dependence and agreed better with experiment. 12 We have attempted to resolve this controversy by mapping out the ozone formation PES with high-level ab initio approaches.…”

“…The new Dawes-LolurLi-Jiang-Guo (DLLJG) PES, obtained with a dynamically weighted 23,24 explicitly-correlated multi-reference configuration interaction [25][26][27] approach with the Davidson correction 28 and spin-orbit correction (DW-MRCI-F12+Q), is "reef"-free, thus qualitatively different from all previous ozone PESs. 16,20,29 The disappearance of the "reef" structure essentially results from the employment of a large basis set, larger active configuration spaces, and dynamical weighting of excited states. Further evidence for the absence of a reef was provided by Tyuterev et al, who found improved agreement with experiment for the highest lying known vibrational levels when a "Dawes correction" to remove the reef was applied to their PES.…”

New analytical model for the ozone electronic ground state potential surface and accurate ab initio vibrational predictions at high energy range

“…Considerable effort has been devoted to the determination of PES in the X 1 A 1 ground electronic state by ab initio calculations [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] or by fitting to experimental rovibrational data. [36][37][38] Global 3D ozone surfaces designed for dynamical calculations have been constructed by Yamashita et al 24 and more accurately by Siebert,Schinke,and Bittererova 20,21 (the corresponding PES is usually referred to as SSB PES).…”

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

“…The low-lying vibrational levels on the SSB PES are very realistic matching experiment to a root-mean-squared error (RMSE) of ∼ 4 cm −1 for levels up to 4000 cm −1 above the ZPE. 12 Straightforward application of the MRCI method at this basis set level does not perform so well and the recent (2013) PES of Ayouz and Babikov 27 employing the same (12,9) reference space, but extrapolating the MRCI data to the CBS limit (MRCI/CBS) overshoots the fundamentals ν 1 and ν 3 by roughly 20 and 30 cm −1 , respectively, with larger errors recorded for overtones and combinations. Those results closely match our unpublished tests in which we have produced accurate fits at the MRCI/CBS level.…”

“…(a value very similar to previous reports), 12 with an energy of 10 755.1 cm −1 (1580 cm −1 above D e , see the supplementary material 32 ). We calculated the low-lying vibrational levels (up to 4000 cm −1 above ZPE) for the 16 27 The other bond is fixed at r 1 = 2.282 a.u. and the angle is fixed at θ = 116.75 • .…”