Shape resonances in the photoionization of cyanogen

Abstract

We have studied the photoionization cross sections and photoelectron asymmetry parameters for ionization of the 1πg(X 2Πg), 5σg(A 2Σ+g), and 4σu(B 2Σ+u) levels of cyanogen using frozen-core Hartree–Fock photoelectron continuum orbitals. The main purpose of these studies has been to extend our understanding of the dynamics of shape resonances from earlier studies of diatomic and smaller polyatomic molecules to a larger polyatomic system. The results do, in fact, reveal a rich shape resonant structure in the electronic continuum of this polyatomic system. There is a low-energy σu resonance which, as expected, is the C–C analog of the l=3 shape resonance seen in N2(3σ−1g) and several other diatomics. In contrast to this diatomic-like behavior, the presence of the two CN groups in C2N2 results in a second σu and a σg resonance corresponding to linear combinations of a l=3 shape resonance localized on the CN sites. Moreover, our results also show a pronounced shape resonant behavior in the πu continuum, which, to our knowledge, has not been seen in smaller molecules.