This paper reports calculations of the rate of isomerization of HCN - 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 ...This paper reports calculations of the rate of isomerization of HCN - 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.展开更多
The classical theory of the rate of unimolecular isomerization developed by Gray and Rice as extended by Zhao and Rice is applied to the calculation of the rate of isomerization in model systems which have linear asym...The classical theory of the rate of unimolecular isomerization developed by Gray and Rice as extended by Zhao and Rice is applied to the calculation of the rate of isomerization in model systems which have linear asymmetric double well potentials. We are interested in this system for two reasons. First, we are interested in the detailed dynamical processes for the mentioned system because it is widely related to practical chemical reactions. Second, the present model system has an asymmetric double well potential, which provides a different test of the accuracy of the approximations used in the Gray-Zhao-Rice theory than posed by previous applications. We have calculated relaxation rates and relaxation times for the model systems on different time scales. We find that for the systems under studies the Gray-Zhao-Rice version of the classical theory of isomerization rate yields values in good agreement with those generated from trajectory calculations and from the Reactive Island theory of De Leon et al.展开更多
文摘This paper reports calculations of the rate of isomerization of HCN - 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.
文摘The classical theory of the rate of unimolecular isomerization developed by Gray and Rice as extended by Zhao and Rice is applied to the calculation of the rate of isomerization in model systems which have linear asymmetric double well potentials. We are interested in this system for two reasons. First, we are interested in the detailed dynamical processes for the mentioned system because it is widely related to practical chemical reactions. Second, the present model system has an asymmetric double well potential, which provides a different test of the accuracy of the approximations used in the Gray-Zhao-Rice theory than posed by previous applications. We have calculated relaxation rates and relaxation times for the model systems on different time scales. We find that for the systems under studies the Gray-Zhao-Rice version of the classical theory of isomerization rate yields values in good agreement with those generated from trajectory calculations and from the Reactive Island theory of De Leon et al.
