Quantum Monte Carlo Study of the Water Dimer Binding Energy and Halogen-pi Interactions

摘要

Halogen-pi systems are involved with competition between halogen bonding and pi-interaction. Using the diffusion quantum Monte Carlo (DMC) method, we compare the interaction of benzene with diatomic halogens (X-2: Cl-2/Br-2) with the typical hydrogen bonding in the water dimer, taking into account explicit correlations of up to three bodies. The benzene-Cl-2/Br-2 binding energies (13.07 +/- 0.42/16.62 +/- 0.02 kJ/mol) attributed to both halogen bonding and dispersion are smaller than but comparable to the typical hydrogen bonding in the water dimer binding energy (20.88 +/- 0.27 kJ/mol). All of the above values are in good agreement with those from the coupled-cluster with single, double, and noniterative triple excitations (CCSD(T)) results at the complete basis set limit (benzene-Cl-2/Br-2: 12.78/16.17 kJ/mol; water dimer: 21.0 kJ/mol).