Variable-Energy Photoelectron Spectroscopy of (eta(5)-C(5)H(5))NiNO: Molecular Orbital Assignment and Xalpha-SW Calculations.

Abstract

Variable-energy valence and inner-valence photoelectron spectra have been recorded for the CpNiNO complex (Cp = eta(5)-C(5)H(5)) between 21.2 and 100 eV, using He I radiation and synchrotron radiation. The ground state electronic structure has been calculated by using the Xalpha-SW method. Photoionization cross sections (sigma) have also been calculated for the valence ionizations using the Xalpha-SW method. The theoretical branching ratios (sigma(i)/ summation operatorsigma) have been compared with the observed branching ratios (A(i)()/ summation operatorA) between 21.2 and 100 eV. The assignment of the photoelectron spectrum based on the analysis of intensity variations and width of vibrational peaks is consistent with the ion state orbital ordering 5e(1)(1) < 7a(1)(2) < 3e(2)(3) < 4e(1)(4) (band numbers are in parentheses) and is inconsistent with another recently proposed ordering 5e(1)(1), 5e(1)(2) < 7a(1), 3e(2)(3) < 4e(1)(4), which takes the 5e(1) vibronic effects into consideration. The experimental branching ratio results indicate a Ni 3p resonance effect around 75 eV in the photoionization process. The inner-valence spectrum has also been assigned with the aid of the Xalpha-SW calculations.