title: The NICS-XY-scan: identification of local and global ring currents in multi-ring systems.
abstract: Nucleus-independent chemical shift (NICS)-based methods are very popular for the determination of the induced magnetic field under an external magnetic field. These methods are used mostly (but not only) for the determination of the aromaticity and antiaromaticity of molecules and ions, both qualitatively and quantitatively. The ghost atom that serves as the NICS probe senses the induced magnetic field and reports it in the form of an NMR chemical shift. However, the source of the field cannot be determined by NICS. Thus, in a multi-ring system that may contain more than one induced current circuit (and therefore more than one source of the induced magnetic field) the NICS value may represent the sum of many induced magnetic fields. This may lead to wrong assignments of the aromaticity (and antiaromaticity) of the systems under study. In this paper, we present a NICS-based method for the determination of local and global ring currents in conjugated multi-ring systems. The method involves placing the NICS probes along the X axis, and if needed, along the Y axis, at a constant height above the system under study. Following the change in the induced field along these axes allows the identification of global and local induced currents. The best NICS type to use for these scans is NICSπZZ , but it is shown that at a height of 1.7 Å above the molecular plane, NICSZZ provides the same qualitative picture. This method, namely the NICS-XY-scan, gives information equivalent to that obtained through current density analysis methods, and in some cases, provides even more details.
authors.affiliation: Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000 (Israel).
authors.forename: Renana
authors.initials: R
authors.lastname: Gershoni-Poranne
authors.forename: Amnon
authors.initials: A
authors.lastname: Stanger
keywords: NICS; aromaticity; density functional calculations; global ring currents; local ring currents; polycycles