Broken symmetry approach and chemical susceptibility of carbon nanotubes



Constituting a part of odd electrons that are excluded from the covalent bonding, effectively unpaired electrons are posed by the singlet instability of the single-determinant broken spin-symmetry unrestricted Hartree–Fock (UBS HF) SCF solution. The correct determination of the total number of effectively unpaired electrons ND and its fraction on each N atom is well provided by the UBS HF solution. The N value is offered to be a quantifier of atomic chemical susceptibility (or equivalently, reactivity) thus highlighting targets that are the most favorable for addition reactions of any type. The approach is illustrated for two families involving fragments of arm-chair (n,n) and zigzag (m,0) single-walled nanotubes different by the length and end structure. Short and long tubes as well as tubes with capped end and open end, in the latter case, both hydrogen terminated and empty, are considered. Algorithms of the quantitative description of any length tubes are suggested. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010