Ligand effects on single-electron transfer of isolated iron atoms in the gaseous complexes [(OC)(m)Fe(OH2)(n)](+) (m, n=0-2, m plus n=1, 2)

0388913 - ÚOCHB 2013 RIV NL eng J - Journal Article
Karlický, F. - Otyepka, M. - Schröder, Detlef
Ligand effects on single-electron transfer of isolated iron atoms in the gaseous complexes [(OC)(m)Fe(OH2)(n)](+) (m, n=0-2, m plus n=1, 2).
International Journal of Mass Spectrometry. Roč. 330, 15 Dec (2012), s. 95-99. ISSN 1387-3806. E-ISSN 1873-2798
R&D Projects: GA ČR GBP208/12/G016
Grant - others:GA ČR(CZ) GPP208/11/P463; European Regional Development Fund(XE) CZ.1.05/2.1.00/03.0058; GA MŠk(CZ) EE2.3.20.0017
Program: EE
Institutional support: RVO:61388963
Keywords : electron transfer * iron carbonyl * microhydration * neutralization-reionization mass * spectrometry * redox transitions
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 2.142, year: 2012

The properties of neutral and monocationic complexes of iron with one and two water or carbonyl ligands (i.e. FeCO0/+, Fe(OH2)(0/+), (OC)Fe(OH2)(0/+), and (H2O)Fe(OH2)(0/+)) are studied by means of wave-function based ab initio theory. Not surprisingly, the addition of ligands to the metal center drastically changes the energetics of the cationic species, whereas the ligation of neutral iron has much smaller effects and the interaction is even repulsive for some neutral quintet states. As a consequence, the associated adiabatic and vertical transitions between the manifold of the neutral and monocationic species experience substantial changes with differences exceeding 1 eV in the ionization energies. The results are used to explain the results of earlier studies of (OC)Fe(OH2)(0/+). and (H2O)Fe(OH2)(0/+) by means of neutralization-reionization mass spectrometry.
Permanent Link: http://hdl.handle.net/11104/0217889