Accurate Calculation of Zero-Field Splittings of (Bio)inorganic Complexes: Application to an {FeNO}7 (S = 3/2) Compound
Iron nitrosyl complexes with {FeNO}7 (S = 3/2) configuration have a complex electronic structure and display remarkable but not fully understood spectroscopic properties. In particular, {FeNO}7 (S = 3/2) complexes have very large zero-field splittings (ZFSs), which arise from strong spin−orbit coupl...
Gespeichert in:
Veröffentlicht in: | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2009-08, Vol.113 (32), p.9150-9156 |
---|---|
Hauptverfasser: | , |
Format: | Artikel |
Sprache: | eng |
Schlagworte: | |
Online-Zugang: | Volltext |
Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
Zusammenfassung: | Iron nitrosyl complexes with {FeNO}7 (S = 3/2) configuration have a complex electronic structure and display remarkable but not fully understood spectroscopic properties. In particular, {FeNO}7 (S = 3/2) complexes have very large zero-field splittings (ZFSs), which arise from strong spin−orbit coupling, a relativistic effect. The accurate prediction and microscopic interpretation of ZFSs in transition metal complexes can aid in the interpretation of a vast amount of spectroscopic (e.g., Mössbauer and electron paramagnetic resonance) and other experimental (e.g., magnetic susceptibility) data. We report the accurate calculation of the sign and magnitude of ZFSs for a set of representative diatomic molecules based on a combined spin density functional theory and perturbation theory (SDFT-PT) methodology. In addition, we apply the SDFT-PT methodology to accurately calculate the magnitude and sign of the ZFS parameters of an {FeNO}7 (S = 3/2) complex and to interpret its spectrocopic data. We find that the principal component D zz of the ZFS tensor is very closely oriented along the Fe−N(O) bond, indicating that nitric oxide dominates the very intricate electronic structure of the {FeNO}7 (S = 3/2) compound. We find a direct correlation between electronic delocalization along the Fe−N(O) bond, which is due to π-bonding, and the large ZFS. |
---|---|
ISSN: | 1089-5639 1520-5215 |
DOI: | 10.1021/jp8107667 |