The dynamics of the ClO + ClO (+N2) radical complex (or chaperon) mechanism is studied by electronic structure methods and quasi-classical trajectory calculations. The geometries and frequencies of the stationary points on the potential energy surface (PES) are optimized at the B3LYP/6-311+G(3df) level of theory, and the energies are refined at the CCSD(T)/6-311+G(3df) (single-point) level of theory. Basis set superposition error (BSSE) corrections are applied to obtain 1.5 kcal mol-1 for the binding energy of the ClO‚N2 van der Waals (VDW) complex. A model PES is developed and used in quasi-classical trajectory calculations to obtain the capture rate constant and nascent energy distributions of ClOOCl* produced via the chaperon mechanism. A range of VDW binding energies from 1.5 to 9.0 kcal mol-1 are investigated. The anisotropic PES for the ClO‚N2 complex and a separable anharmonic oscillator approximation are used to estimate the equilibrium constant for formation of the VDW complex. Rate constants, branching ratios to produce ClOOCl, and nascent energy distributions of excited ClOOCl* are discussed with respect to the VDW binding energy and temperature. Interestingly, even for weak VDW binding energies, the N2 usually carries away enough energy to stabilize the nascent ClOOCl*, although the VDW equilibrium constant is small. For stronger binding energies, the stabilization efficiency is reduced, but the capture rate constant is increased commensurately. The resulting rate constants for forming ClOOCl* from the title reaction are only weakly dependent on the VDW binding energy and temperature. As a result, the relative importance of the chaperon mechanism is mostly dependent on the VDW equilibrium constant. For the calculated ClO‚N2 binding energy of 1.5 kcal mol-1, the VDW equilibrium constant is small, and the chaperon mechanism is only important at very high pressures.