Dynamics of electronic energy quenching: The reaction of H2(B)+He

Abstract

The room temperature rate constants for quenching of the fluorescence of H2, HD, and D2 B1Σ+u by 4He have been measured as a function of the initially excited rotational and vibrational levels of the hydrogen molecule. The effective quenching cross sections increase with increasing vibrational energy from about 1 Å2 up to a maximum of about 6 Å2. The effective cross sections for D2 (B, v′ = 0) were independent of the rotational level excited for 0 < J′ ≤ 7, and the cross sections for (v′ = 0, J′ = 0) were about 80% of the values for (v′ = 0, J′ ≳ 0) for all three isotopes studied. Quenching occurs via formation of an electronically excited (H2He)* collision complex followed by crossing to the repulsive H2(X)–He potential energy surface. The vibrational state dependence of the quenching cross sections fits a vibrationally adiabatic model for complex formation. From the vibrational state dependence of the quenching cross section, the barrier height for the quenching reaction is found to be 250±40 cm−1, and the difference in the H–H stretching frequencies between H2(B) and the H2–He complex at the barrier to reaction is 140±80 cm−1. Both values are substantially smaller than results from ab initio calculations. The rotational state dependence of the quenching cross sections suggests that quenching occurs with H2 rotating in a plane perpendicular to the relative velocity vector, in qualitative agreement with the rotational anisotropy of the H2(B)–He ab initio electronic potential energy surface.