Abstract
This work presents two global triplet potential energy surfaces (PESs) for the highenergy reaction N_{2}(X^{1}Σ) + O(^{3}P) → NO(X^{2}Π) + N(^{4}S)  in particular, for the lowest energy ^{3}A′ and ^{3}A″ PESs. In order to obtain the energies needed for fitting analytic surfaces, we carried out multireference configuration interaction (MRCI) calculations based on wave functions obtained from stateaveraged complete active space selfconsistent field calculations for 2280 geometries for the three lowest ^{3}A″ states and for 2298 geometries for the three lowest ^{3}A′ states. The lowestenergy ^{3}A′ and ^{3}A″ states at each of these geometries were then improved by applying the dynamically scaled external correlation (DSEC) method to all MRCI points, and the resulting DSEC energies were used for construction of the groundstate PES for each symmetry. The manybody component of the DSEC energies for the threedimensional ^{3}A′ and ^{3}A″ PESs was then leastsquares fitted in terms of permutationally invariant polynomials in mixed exponentialGaussian bond order variables. The global and local minima as well as the transition structures of both the ^{3}A′ and the ^{3}A″ analytic PES were explored. In agreement with previous work, we find that the reverse reaction is barrierless on the ^{3}A″ surface along the minimum energy pathway. However, we have explored several new local minima and transition structures on the ^{3}A′ PES. Furthermore, based on the newly found minima and transition structures, two independent reaction mechanisms have been illustrated for the reaction path on the ^{3}A′ PES. The analytic surfaces may be used for dynamics calculations of electronically adiabatic reactive scattering and energy transfer.
Original language  English (US) 

Article number  024309 
Journal  Journal of Chemical Physics 
Volume  144 
Issue number  2 
DOIs  
State  Published  Jan 14 2016 
Bibliographical note
Publisher Copyright:© 2016 AIP Publishing LLC.
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Dive into the research topics of 'Global triplet potential energy surfaces for the N<sub>2</sub>(X <sup>1</sup>Σ) + O(<sup>3</sup> P) → NO(X <sup>2</sup>Π) + N(<sup>4</sup> S) reaction'. Together they form a unique fingerprint.Datasets

Electronic structure data for ³A' and A" N₂O
Truhlar, D. G., Lin, W., Varga, Z., Song, G. & Paukku, Y., Data Repository for the University of Minnesota, 2020
DOI: 10.13020/c66z2z26, http://hdl.handle.net/11299/216938
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