Noble gas matrix effects on the equilibrium and transition structures of noble gas molecules: A theoretical study

The noble gas matrix effects on the equilibrium and transition structures of 29 noble gas molecules were simulated at the MP2(FC) level within the framework of polarizable continuum model with integral equation formalism (IEF-PCM). The T1 diagnostic and the largest amplitude of the optimized gas-phase and matrix-solvation equilibrium and transition structures of the 29 noble gas molecules were calculated by the CCSD method so as to assess the multi-reference character or the quality of the optimized structures. For all of the 29 noble gas molecules, the dipole moment of the gaseous transition structure is significantly larger than that of the gaseous equilibrium structure. The reaction barrier of the dissociation channel XNgY → Ng + XY decreases noticeably (by 13–50%) upon the matrix effect modeling, indicating that the kinetic stability of the gaseous noble gas molecules is probably higher than that of the noble gas molecules solvated or isolated in the noble gas matrix.