Effect of intramolecular energy transfer on the rate of unimolecular isomerization: HCN reversible HNC

摘要

This paper reports calculations of the rate of isomerization of HCN reversible HCN based on the theory of Gary and Rice as extended by Zhao and Rice. The major task is to determine the effect of intramolecular energy transfer on the prediction of the rate of isomerization. Both the full three-dimensional (3D) system and the reduced two-dimensional (2D) system obtained from freezing CN bond at 1.159 A are analyzed to check the validity of the freezing bond approximation. Meanwhile, RRKM rates are calculated to test RRKM choice of the transition state by comparing to Gary-Rice three-state model. The comparison shows that the rates from 2D model and 3D model are differing up to 20% with 2D rates consistently larger. The intramolecular energy transfer modifies the isomerization rate for HCN system up to 30% that is modestly small by the expectation. The isomerization rate predicted from RRKM theory is greater than those of Gary-Rice three-state model theory up to 65%, and it overstimates the rates under all considerations, including the contribution from intramolecular energy transfer, for the studied system by about a factor of 2.