Tuning out vibrational levels in molecular electron energy-loss spectra

Abstract

The phenomenon whereby features associated with certain vibrational levels in molecular states of mixed electronic character disappear under specific scattering conditions in electron energy-loss spectra is investigated. In particular, using a combination of experimental measurements and coupled-channel calculations, anomalous vibrational intensities in the mixed valence-Rydberg 1Π u←X1Σg+ transition of N 2 are explained. A single parameter, i.e., the ratio of the generalized electronic transition moments to the diabatic valence and Rydberg components of the mixed states, dependent on the experimental scattering conditions, is found to be essentially capable of describing all observed relative vibrational intensities, including the near disappearance of the b1Π u(v=5) feature for momentum-transfer-squared values K2 ≈ 0.3 a.u. This result highlights the interesting possibility of experimental control of molecular quantum-interference effects in electron energy-loss spectra, something that is not possible in optical spectra.