The hydrogen abstraction reaction from H_(2)S by OH is of key importance in understanding of the causes of acid rain,air pollution,and climate change.In this work,the reaction OH+H_(2)S→H_(2)O+SH is investigated on a...The hydrogen abstraction reaction from H_(2)S by OH is of key importance in understanding of the causes of acid rain,air pollution,and climate change.In this work,the reaction OH+H_(2)S→H_(2)O+SH is investigated on a recently developed ab initio-based globally accurate potential energy surface by the time-dependent wave packet approach under a reduceddimensional model.This reaction behaves like a barrier-less reaction at low collision energies and like an activated reaction with a well-defined barrier at high collision energies.Exciting either the symmetric or antisymmetric stretching mode of the molecule H_(2)S enhances the reactivity more than exciting the bending mode,which is rationalized by the coupling strength of each normal mode with the reaction coordinate.In addition,the modespecific rate constant shows a remarkable non-Arrhenius temperature dependence.展开更多
Assuming that the main variables in the life processes at the molecular level are the conforma- tion of biological macromolecules and their frontier electrons a formalism of quantum theory on conformation-electron sys...Assuming that the main variables in the life processes at the molecular level are the conforma- tion of biological macromolecules and their frontier electrons a formalism of quantum theory on conformation-electron system is proposed. Based on the quantum theory of conformation-electron system, the protein folding is regarded as a quantum transition between torsion states on polypep- tide chain, and the folding rate is calculated by nonadiabatic operator method. The rate calculation is generalized to the case of frequency variation in folding. An analytical form of protein folding rate formula is obtained, which can be served as a useful tool for further studying protein folding. The application of the rate theory to explain the protein folding experiments is briefly summarized. It includes the inertial moment dependence of folding rate, the unified description of two-state and multistate protein folding, the relationship of folding and unfolding rates versus denaturant concen- tration, the distinction between exergonic and endergonic foldings, the ultrafast and the downhill folding viewed from quantum folding theory, and, finally, the temperature dependence of folding rate and the interpretation of its non-Arrhenius behaviors. All these studies support the view that the protein folding is essentially a quantum transition between conformational states.展开更多
基金supported by the National Natural Science Foundation of China(No.21973109 to Hongwei Song,No.21773297,No.21973108,and No.21921004 to Minghui Yang)the Ministry of Education,Singapore,under its Academic Research Fund Tier 1(RG83/20)to Yunpeng Lu。
文摘The hydrogen abstraction reaction from H_(2)S by OH is of key importance in understanding of the causes of acid rain,air pollution,and climate change.In this work,the reaction OH+H_(2)S→H_(2)O+SH is investigated on a recently developed ab initio-based globally accurate potential energy surface by the time-dependent wave packet approach under a reduceddimensional model.This reaction behaves like a barrier-less reaction at low collision energies and like an activated reaction with a well-defined barrier at high collision energies.Exciting either the symmetric or antisymmetric stretching mode of the molecule H_(2)S enhances the reactivity more than exciting the bending mode,which is rationalized by the coupling strength of each normal mode with the reaction coordinate.In addition,the modespecific rate constant shows a remarkable non-Arrhenius temperature dependence.
文摘Assuming that the main variables in the life processes at the molecular level are the conforma- tion of biological macromolecules and their frontier electrons a formalism of quantum theory on conformation-electron system is proposed. Based on the quantum theory of conformation-electron system, the protein folding is regarded as a quantum transition between torsion states on polypep- tide chain, and the folding rate is calculated by nonadiabatic operator method. The rate calculation is generalized to the case of frequency variation in folding. An analytical form of protein folding rate formula is obtained, which can be served as a useful tool for further studying protein folding. The application of the rate theory to explain the protein folding experiments is briefly summarized. It includes the inertial moment dependence of folding rate, the unified description of two-state and multistate protein folding, the relationship of folding and unfolding rates versus denaturant concen- tration, the distinction between exergonic and endergonic foldings, the ultrafast and the downhill folding viewed from quantum folding theory, and, finally, the temperature dependence of folding rate and the interpretation of its non-Arrhenius behaviors. All these studies support the view that the protein folding is essentially a quantum transition between conformational states.
