The Decay of Dispersion Interaction and Its Remarkable Effects on the Kinetics of Activation Reactions Involving Alkyl Chains.

Abstract

The importance of dispersion interactions in many chemical processes is well recognized. It is known that the dispersion strength would decay with the increasing separation between the interacting groups; however, its effects on chemical reactivity have not been well understood. Here we reveal the decay law of dispersion interactions along the n-alkyl chain, its effective interaction ranges for common functional groups, and their remarkable effects on the kinetics of activation reactions involving alkyl chains. This is achieved by DLPNO-CCSD(T) calculations and the local energy decomposition analysis and is supported by experimental findings. In particular, our calculations indicate that the lifetime of alkyl-substituted cis-azobenzenes increases with the alkyl chain length but reaches a steady value when alkyl chains are longer than butyl groups, which is in satisfactory accordance with experimental measurements. We also propose a concise expression to describe the dispersion decay, which shows excellent agreement with our computed results.