Development, simulation, and validation of NMR relaxation-based exchange measurements
Two-dimensional (2D) nuclear magnetic resonance correlation experiments have recently been proposed as a means for studying exchange in porous media. Most notable of these is the T2−T2 relaxatio...
Two-dimensional (2D) nuclear magnetic resonance correlation experiments have recently been proposed as a means for studying exchange in porous media. Most notable of these is the T2−T2 relaxatio...
Theoretical studies of UO2(OH)(H2O)n+, UO2(OH)2(H2O)n, NpO2(OH)(H2O)n, and PuO2(OH)(H2O)n+ (n
21) complexes in aqueous solution
Extensive ab initio calculations have been carried out to study equilibrium structures, vibrational frequencies, and the nature of chemical bonds of hydrated UO2(OH)+, UO2(OH)2, NpO2(OH), and PuO2(OH)...
21) complexes in aqueous solutionExtensive ab initio calculations have been carried out to study equilibrium structures, vibrational frequencies, and the nature of chemical bonds of hydrated UO2(OH)+, UO2(OH)2, NpO2(OH), and PuO2(OH)...
Kinetics of collision-induced reactions between hard-sphere reactants
J. Chem. Phys. 131, 164503 (2009); doi:10.1063/1.3251144
Published 26 October 2009
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We investigate the reaction kinetics of hard-sphere reactants that undergo reaction upon collision. When the reaction probability at a given collision is unity, the Noyes rate theory provides an exact expression of the rate coefficient. For the general case with the reaction probability less than unity, Noyes assumed that successive recollision times between a tagged pair of reactants are decorrelated. We show that with this renewal assumption, the rate theory of Wilemski and Fixman yields the same rate coefficient expression as the Noyes theory. To evaluate the validity of the renewal assumption, we carry out molecular dynamics simulations. Contrary to the usual expectation, we find that the renewal assumption works better at higher particle densities. The present study shows that the rate coefficient for collision-induced hard-sphere reactions can be estimated with great accuracy by using the first recollision time distribution alone, regardless of the magnitude of the reaction probability at a given collision.
©2009 American Institute of Physics
| History: | Received 4 September 2009; accepted 30 September 2009; published 26 October 2009 |
| Permalink: |
http://link.aip.org/link/?JCPSA6/131/164503/1 |
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Connotea
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BibSonomy
KEYWORDS and PACS
molecular dynamics method,
probability,
reaction kinetics theory,
reaction rate constants,
statistical mechanics
- 82.20.Db
Transition state theory and statistical theories of rate constants (chemical kinetics) - 82.20.Fd
Collision theories and trajectory models of chemical kinetics - 82.20.Pm
Chemical rate constants, reaction cross sections, and activation energies - 82.20.Sb
Correlation function theory of rate constants and its applications in chemical kinetics - 82.20.Wt
Computational modeling and simulation of chemical kinetics - YEAR: 2009
RELATED DATABASES
PUBLICATION DATA
0021-9606 (print)
1089-7690 (online)
AIP
REFERENCES (20)
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