Journal of Computational Chemistry
Journal of Computational Chemistry
5 years ago

Canonical orbital contributions to the magnetic fields induced by global and local diatropic and paratropic ring currents

Canonical orbital contributions to the magnetic fields induced by global and local diatropic and paratropic ring currents
Alvaro Muñoz-Castro, Thomas A. Nikopoulos, Anastasios G. Papadopoulos, Michael P. Sigalas, Nickolas D. Charistos
The induced magnetic field (IMF) of naphthalene, biphenyl, biphenylene, benzocyclobutadiene, and pentalene is dissected to contributions from the total π system, canonical π-molecular orbitals (CMO), and HOMOπ* excitations, to evaluate and interpret relative global and local diatropicity and paratropicity. Maps of the IMF of the total π system reveal its relative strength and topology that corresponds to global and local diatropic and paratropic ring currents. The total π magnetic response is determined by this of canonical HOMOs and particularly by paratropic contributions of rotational excitations from HOMOs to unoccupied π* orbitals. Low energy excitations and similar nodal structure of HOMO and π* induce strong paratropic fields that dominate on antiaromatic rings. High energy excitations and different nodal structures lead to weak paratropic contributions of canonical HOMOs, which are overwhelmed by diatropic response of lower energy canonical orbitals in aromatic rings. CMO-IMF analysis is found in agreement with ring current analysis. © 2017 Wiley Periodicals, Inc. The through-space magnetic response of naphthalene, biphenyl, biphenylene, benzocyclobutadiene, and pentalene is dissected to contributions from the total π system, canonical π-molecular orbitals, and rotational HOMOπ* excitations. The characteristic pattern and topology of the magnetic field induced from global and local diatropic and paratropic ring currents are revealed. The induced magnetic field is found to be shaped from ΗΟΜΟπ* excitations depending on the energy gap, symmetry, and nodal structure of interacting orbitals.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/jcc.24917

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