Impact of ionization of ferrocene: EOES of alpha- and beta- electrons and the fingerprint orbital of ferrocenium

TL;DR

This study uses quantum mechanical methods to analyze the ionization of ferrocene, revealing that electron removal does not alter geometry but significantly affects the Fe-centered orbitals and energy spectrum, especially in the fingerprint orbital of ferrocenium.

Contribution

It provides detailed insights into the electronic structure and orbital energy changes upon ferrocene ionization, highlighting the role of Fe-electrons and identifying the fingerprint orbital of ferrocenium.

Findings

Ionization causes minimal geometric change (<2%) in ferrocene.

Fe-electrons experience significant energy shifts upon ionization.

The fingerprint orbital 8a1 is identified as key in ferrocenium.

Abstract

Ionization process of ferrocene (Fc) to produce ferrocenium cation (Fc+) has been debated as much as the eclipsed and staggered ferrocene conformers. The present quantum mechanical study reveals that removal of an electron does not apparently affect the geometry and symmetry of the cation, as the geometric changes are < 2% with respect to neutral Fc, but produce the fingerprint orbital 8a1 of Fc+. The excess orbital energy spectrum (EOES) of the \alpha- and \beta-electrons reveals that the electrons originated from the transition metal Fe in both core and valence shells experience significant energy changes in the cation with respect to the neutral ferrocene counterparts, indicating that the Fe-electrons correlate stronger than electrons from other atoms such as carbons in ferrocene. The EOES also exhibits that the orbital energies of the \alpha-electrons in ferrocenium change more significantly than the \beta-electrons after one \beta-electron being ionized with respect to ferrocene. The most significant changes upon ionization are dominated by the Fe-electrons in non-degenerate signature orbitals. That is, 4a1 which is dominated by the Fe 3s orbital, 3a2 by the Fe 3pz orbital and the 8a1 orbital (alpha only) by the Fe 3dz2 (one beta-electron is removed from this orbital). The \Delta DFT and \Delta SCF calculations yield the IP of 6.90 eV and 6.85 eV, respectively, in excellent agreement to the recent measurements of 6.9 \pn 0.1 eV, suggesting that significant relaxation energy exists whereas electron correlation energies are largely cancelled out. A further dual space analysis (DSA) identifies that the momentum profiles of such the singly occupied fingerprint 8a1 orbital indeed experiences most significant changes in all orbitals of Fc+, again indicates that the electron removal of ferrocene ionization is not from the highest occupied molecular orbital.