Vibrationally resolved excitation, dissociation, and rotational cross sections of NH radical by electron-impact using the R-matrix method

Abstract

The ab initio R-matrix method is employed to study the electronic excitation of low-lying target states, the dissociation cross sections, and the rotational cross sections of the NH radical by electron impact for energies up to 15 eV. We have included dynamic interaction in our scattering model that uses close coupling formalism. There are 24 target states whose vertical excitation energies are below 15 eV, which are included in the trial wavefunction of the entire scattering system. In our scattering model, two electrons are frozen in the 1σ2 configuration and the remaining six electrons are free to move in the molecular orbitals 2σ 3σ 4σ 5σ 6σ 1π and 2π. The cc-pVTZ Dunning basis sets are used to optimize the target structure and electron scattering. The vibrationally resolved cross sections for transition from the ground state X 3Σ− to excited state c 1Π are computed by scaling the corresponding electronic excitation cross section by Franck-Condon factors. These factors are evaluated by using accurate potential energy curves of the ground state and the c excited state. We have compared the excitation cross section for the optically allowed transition X 3Σ− to A 3Π computed using our scattering model with the corresponding cross section evaluated in Born approximation, and the agreement is quite good indicating that for a reasonably high transition moment and a low threshold of the excited state, the effects of correlation and polarization are not very significant. The dissociative excitation cross section by electron impact into atomic fragments N and H is also shown which are caused mainly by c 1Π and a purely repulsive state 1 5Σ−. We have also shown that the vibrational cross section evaluated in Born approximation for the fundamental transition 0–1 of the ground state is quite small as compared to the rotational cross sections. The rotational cross sections are computed for j = 0 to j′ = 0–5, and it is shown that the dipole induced transition is predominant with an order of magnitude higher than the pure rotational 0–0 cross section. We have detected many low-lying core-excited shape resonances and provided their resonance parameters which form an important input to estimate dissociative electron attachment cross sections.