The ab initio ipsocentric approach to calculation and mapping of induced orbital current density is extended to open-shell π systems. ROHF/6-31G** calculations document the (magnetic) aromaticity of planar 4nπ triplet states of 4π/8π annulenes and isobenzofulvene, and quintet excited-state azulene. An orbital model for currents rationalises the generalised form of Baird's rules, by which 4n + 2 annulenes are aromatic (antiaromatic) in states of even (odd) total spin (vice versa for 4nπ annulenes). In contrast to geometric criteria, ring-currents predict antiaromaticity for the doublet naphthalene radical anion. © 2007 Elsevier B.V. All rights reserved.
Ring-current aromaticity in open-shell systems
Soncini A.;
2008
Abstract
The ab initio ipsocentric approach to calculation and mapping of induced orbital current density is extended to open-shell π systems. ROHF/6-31G** calculations document the (magnetic) aromaticity of planar 4nπ triplet states of 4π/8π annulenes and isobenzofulvene, and quintet excited-state azulene. An orbital model for currents rationalises the generalised form of Baird's rules, by which 4n + 2 annulenes are aromatic (antiaromatic) in states of even (odd) total spin (vice versa for 4nπ annulenes). In contrast to geometric criteria, ring-currents predict antiaromaticity for the doublet naphthalene radical anion. © 2007 Elsevier B.V. All rights reserved.Pubblicazioni consigliate
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