The lowest-lying electronic singlet and triplet potential energy surfaces (PES) for the HNO–NOH system have been investigated employing high level ab initio quantum chemical methods. The reaction energies and barriers have been predicted for two isomerization and four dissociation reactions. Total energies are extrapolated to the complete basis set limit applying focal point analyses. Anharmonic zero-point vibrational energies, diagonal Born-Oppenheimer corrections, relativistic effects, and core correlation corrections are also taken into account. On the singlet PES, the 1HNO $\longrightarrow$ 1NOH endothermicity including all corrections is predicted to be 42.23 ± 0.2 kcal mol−1. For the barrierless decomposition of 1HNO to H + NO, the dissociation energy is estimated to be 47.48 ± 0.2 kcal mol−1. For 1NOH $\longrightarrow$ H + NO, the reaction endothermicity and barrier are 5.25 ± 0.2 and 7.88 ± 0.2 kcal mol−1. On the triplet PES the reaction energy and barrier including all corrections are predicted to be 7.73 ± 0.2 and 39.31 ± 0.2 kcal mol−1 for the isomerization reaction 3HNO $\longrightarrow$ 3NOH. For the triplet dissociation reaction (to H + NO) the corresponding results are 29.03 ± 0.2 and 32.41 ± 0.2 kcal mol−1. Analogous results are 21.30 ± 0.2 and 33.67 ± 0.2 kcal mol−1 for the dissociation reaction of 3NOH (to H + NO). Unimolecular rate constants for the isomerization and dissociation reactions were obtained utilizing kinetic modeling methods. The tunneling and kinetic isotope effects are also investigated for these reactions. The adiabatic singlet–triplet energy splittings are predicted to be 18.45 ± 0.2 and 16.05 ± 0.2 kcal mol−1 for HNO and NOH, respectively. Kinetic analyses based on solution of simultaneous first-order ordinary-differential rate equations demonstrate that the singlet NOH molecule will be difficult to prepare at room temperature, while the triplet NOH molecule is viable with respect to isomerization and dissociation reactions up to 400 K. Hence, our theoretical findings clearly explain why 1NOH has not yet been observed experimentally.
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See supplementary material at http://dx.doi.org/10.1063/1.4704895 for geometries, harmonic, and anhormonic frequencies, and rate constants for isotopic species.
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