Abstract
The x-ray absorption spectrum of N_{2}^{+} in the K-edge region has been measured by irradiation of ions stored in a cryogenic radio frequency ion trap with synchrotron radiation. We interpret the experimental results with the help of restricted active space multiconfiguration theory. Spectroscopic constants of the 1σ_{u}^{-1} ^{2}Σ_{u}^{+} state, and the two 1σ_{u}^{-1}3σ_{g}^{-1}1π_{g} ^{2}Π_{u} states are determined from the measurements. The charge of the ground state together with spin coupling involving several open shells give rise to double excitations and configuration mixing, and a complete breakdown of the orbital picture for higher lying core-excited states.
Highlights
The x-ray absorption spectrum of Nþ2 in the K-edge region has been measured by irradiation of ions stored in a cryogenic radio frequency ion trap with synchrotron radiation
X-ray absorption spectroscopy (XAS) of small molecular ions can become a powerful technique for fundamental molecular physics, with potential ramifications in several fields
XAS of the molecular ion allows for the observation of highly excited states, which description challenges current theoretical models
Summary
We present the first x-ray absorption spectrum of the Nþ2 ion This is measured with a spectral quality that allows for analysis of the vibrational excitations and for resolving close lying states. The product ions Nþ and N22þ (both having a mass/charge ratio of 14 amu) were used to record the action spectrum of Nþ2 In this case, Nþ=N22þ was the only observed ion signal, and we assume that it is proportional to the x-ray absorption cross section [24,25]. Calculations of the potential energy curves were performed for the states assigned to the features below 405 eV Based on these potential energy curves wave packet calculations were done to predict the vibrational fine structure in the spectra. We assign the fine structure of the first three features to vibronic excitations
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