Niels E. Henriksen and Flemming Y. Hansen
- Published in print:
- 2008
- Published Online:
- January 2010
- ISBN:
- 9780199203864
- eISBN:
- 9780191708251
- Item type:
- chapter
- Publisher:
- Oxford University Press
- DOI:
- 10.1093/acprof:oso/9780199203864.003.0010
- Subject:
- Physics, Condensed Matter Physics / Materials
This chapter discusses static solvent effects on the rate constant for chemical reactions in solution. It starts with a brief discussion of the thermodynamic formulation of transition-state theory. ...
More
This chapter discusses static solvent effects on the rate constant for chemical reactions in solution. It starts with a brief discussion of the thermodynamic formulation of transition-state theory. The static equilibrium structure of the solvent will modify the potential energy surface for the chemical reaction. This effect is analyzed within the framework of transition-state theory. The rate constant is expressed in terms of the potential of mean force at the activated complex. Various definitions of this potential and their relations to n-particle- and pair-distribution functions are considered. The potential of mean force may, for example, be defined such that the gradient of the potential gives the average force on an atom in the activated complex, Boltzmann averaged over all configurations of the solvent. It concludes with a discussion of a relation between the rate constants in the gas phase and in solution.Less
This chapter discusses static solvent effects on the rate constant for chemical reactions in solution. It starts with a brief discussion of the thermodynamic formulation of transition-state theory. The static equilibrium structure of the solvent will modify the potential energy surface for the chemical reaction. This effect is analyzed within the framework of transition-state theory. The rate constant is expressed in terms of the potential of mean force at the activated complex. Various definitions of this potential and their relations to n-particle- and pair-distribution functions are considered. The potential of mean force may, for example, be defined such that the gradient of the potential gives the average force on an atom in the activated complex, Boltzmann averaged over all configurations of the solvent. It concludes with a discussion of a relation between the rate constants in the gas phase and in solution.
Niels Engholm Henriksen and Flemming Yssing Hansen
- Published in print:
- 2018
- Published Online:
- November 2018
- ISBN:
- 9780198805014
- eISBN:
- 9780191843129
- Item type:
- chapter
- Publisher:
- Oxford University Press
- DOI:
- 10.1093/oso/9780198805014.003.0010
- Subject:
- Physics, Atomic, Laser, and Optical Physics
This chapter discusses static solvent effects on the rate constant for chemical reactions in solution. It starts with a brief discussion of the thermodynamic formulation of transition-state theory. ...
More
This chapter discusses static solvent effects on the rate constant for chemical reactions in solution. It starts with a brief discussion of the thermodynamic formulation of transition-state theory. The static equilibrium structure of the solvent will modify the potential energy surface for the chemical reaction. This effect is analyzed within the framework of transition-state theory. The rate constant is expressed in terms of the potential of mean force at the activated complex. Various definitions of this potential and their relations to n-particle- and pair-distribution functions are considered. The potential of mean force may, for example, be defined such that the gradient of the potential gives the average force on an atom in the activated complex, Boltzmann averaged over all configurations of the solvent. It concludes with a discussion of a relation between the rate constants in the gas phase and in solution.Less
This chapter discusses static solvent effects on the rate constant for chemical reactions in solution. It starts with a brief discussion of the thermodynamic formulation of transition-state theory. The static equilibrium structure of the solvent will modify the potential energy surface for the chemical reaction. This effect is analyzed within the framework of transition-state theory. The rate constant is expressed in terms of the potential of mean force at the activated complex. Various definitions of this potential and their relations to n-particle- and pair-distribution functions are considered. The potential of mean force may, for example, be defined such that the gradient of the potential gives the average force on an atom in the activated complex, Boltzmann averaged over all configurations of the solvent. It concludes with a discussion of a relation between the rate constants in the gas phase and in solution.
