Electronic structure of the chlorine pseudohalides ClNCO and ClNNN

Abstract
The electronic structure of the ground states of chlorine isocyanate and chlorine azide is investigated using ab initio LCAO–MO–SCF calculations with a moderately large basis. The difference in strength of the Cl—N bond for the two compounds is found to be caused by a greater contribution from the N s orbital of the azide. The calculations also show that the total charge on chlorine in these compounds is positive.

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