We present both the BornOppenheimer (BO) and the nonadiabatic (NA) conical-intersection quantum dynamics of the title reactions, (1) and (2), respectively. BO or NA calculations are carried out using adiabatic or diabatic electronic states, respectively, and we consider some vibrational (v0) and rotational (j0) states of O2, taking into account the Pauli principle. The results reflect the barrier or barrierless nature of reaction (1) or (2), respectively, and the former is, thus, much less reactive than the latter. Reaction (1) is direct and its probabilities and cross sections increase with the collision energy from a threshold value, are slightly affected by NA couplings only at high energies, increase with v0, and are essentially unchanged by j0. On the contrary, reaction (2) is indirect and its probabilities and cross sections decrease with the collision energy without any threshold, are significantly lowered by NA couplings at low energies, and decrease with both v0 and j0.
Quantum calculations of nonadiabatic 2A1-2B2 conical-intersection effects in the reactions N(4S)+O2(X3Sigmag-) and N(4S)+O2(A3Deltau)
C Petrongolo
2010
Abstract
We present both the BornOppenheimer (BO) and the nonadiabatic (NA) conical-intersection quantum dynamics of the title reactions, (1) and (2), respectively. BO or NA calculations are carried out using adiabatic or diabatic electronic states, respectively, and we consider some vibrational (v0) and rotational (j0) states of O2, taking into account the Pauli principle. The results reflect the barrier or barrierless nature of reaction (1) or (2), respectively, and the former is, thus, much less reactive than the latter. Reaction (1) is direct and its probabilities and cross sections increase with the collision energy from a threshold value, are slightly affected by NA couplings only at high energies, increase with v0, and are essentially unchanged by j0. On the contrary, reaction (2) is indirect and its probabilities and cross sections decrease with the collision energy without any threshold, are significantly lowered by NA couplings at low energies, and decrease with both v0 and j0.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
