Cis → trans , trans→cis isomerizations and N–O bond dissociation of nitrous acid (HONO) on an ab initio potential surface obtained by novelty sampling and feed-forward neural network fitting

Abstract

The isomerization and dissociation dynamics of HONO are investigated on an ab initio potential surface obtained by fitting the results of electronic structure calculations at 21 584 configurations by using previously described novelty sampling and feed-forward neural network (NN) methods. The electronic structure calculations are executed by using GAUSSIAN 98 with a 6-311G(d) basis set at the MP4(SDQ) level of accuracy. The average absolute error of the NN fits varies from 0.012 eV (1.22 kJ mol(-1)) to 0.017 eV (1.64 kJ mol(-1)). The average computation time for a HONO trajectory using a single NN surface is approximately 4.8 s. These computation times compare very favorably with those required by other methods primarily because the NN fitting needs to be executed only one time rather than at every integration point. If the average result obtained from a committee of NNs is employed at each point rather than a single NN, increased fitting accuracy can be achieved at the expense of increased computational requirements. In the present investigation, we find that a committee comprising five NN potentials reduces the average absolute interpolation error to 0.0111 eV (1.07 kJ mol(-1)). Cis-trans isomerization rates with total energy of 1.70 eV (including zero point energy) have been computed for a variety of different initial distributions of the internal energy. In contrast to results previously reported by using an empirical potential, where cis-->trans to trans-->cis rate coefficient ratios at 1.70 eV total energy were found to lie in the range of 2.0-12.9 depending on the vibration mode excited, these ratios on the ab initio NN potential lie in the range of 0.63-1.94. It is suggested that this result is a reflection of much larger intramode coupling terms present in the ab initio potential surface. A direct consequence of this increased coupling is a significant decrease in the mode specific rate enhancement when compared to results obtained by using empirical surfaces. All isomerizations are found to be first order in accordance with the results reported by using empirical potentials. The dissociation rate to NO+OH has been investigated at internal HONO energies of 3.10 and 3.30 eV for different distributions of this energy among the six vibrational modes of HONO. These dissociations are also found to be first order. The computed dissociation rate coefficients exhibit only modest mode specific rate enhancement that is significantly smaller than that obtained on an empirical surface because of the much larger mode couplings present on the ab initio surface.