On the Unimolecular Decomposition of the tert-Butoxy Radical

1973 ◽  
Vol 51 (13) ◽  
pp. 2138-2140 ◽  
Author(s):  
C. K. Yip ◽  
H. O. Pritchard
Keyword(s):  
Pressure Dependence ◽  
Unimolecular Reaction ◽  
Unimolecular Decomposition ◽  
Reaction Theory ◽  
Butoxy Radical

It is argued that a large apparent pressure dependence in the rate of decomposition of the tert-butoxy radical should not be interpreted in terms of unimolecular reaction theory; the effect is probably heterogeneous in origin.

The commutative property of strong-transition rate matrices

1979 ◽  
Vol 57 (21) ◽  
pp. 2793-2797 ◽  
Author(s):  
Huw O. Pritchard ◽  
Arunachalam Lakshmi
Keyword(s):  
Transition Rate ◽  
Transition Probabilities ◽  
Boltzmann Distribution ◽  
Unimolecular Reaction ◽  
Infinite Time ◽  
Relaxation Matrix ◽  
Reaction Theory ◽  
Strong Transition ◽  
Commutative Property

The (n − 1)-fold degenerate set of transition probabilities used in our recent reformulation of unimolecular reaction theory is operationally equivalent to the set of effective strong-transition probabilities introduced recently by Nordholm. We have found that the relaxation matrix corresponding to these transition probabilities commutes with any other relaxation matrix which will drive the same system to a Boltzmann distribution at infinite time. Some useful results stemming from this commutative property are presented; we expect that these results will help to clarify further the nature of the assumptions underlying strong- and effective strong-collision theories.

scholarly journals On the Question of Mode-Specificity in Unimolecular Reaction Dynamics

1983 ◽  
Vol 2 (5-6) ◽  
pp. 243-252 ◽  
Author(s):  
William H. Miller
Keyword(s):  
Transition State ◽  
Coupled Oscillators ◽  
Laser Excitation ◽  
Model Problem ◽  
Significant Degree ◽  
Decay Rates ◽  
Unimolecular Reaction ◽  
Unimolecular Decomposition ◽  
Planar Transition ◽  
Mode Specificity

Unimolecular decomposition following state-specific laser excitation is considered. If the transition state for the unimolecular reaction possesses any geometrical symmetry, then it is shown that this can lead to mode-specificity in the decay rates (i.e., different states with essentially the same total energy and angular momentum react at significantly different rates). This is illustrated for a model problem of two coupled oscillators (the Henon–Heiles potential) and also for the unimolecular dissociation of formaldehyde, H2CO→H2+CO, which has a planar transition state. Dynamical calculations indicate that there may also be a significant degree of mode-specificity for the formaldehyde reaction beyond that due to symmetry.

Decomposition of the t‐Butoxy Radical; Evidence for Pressure Dependence

1962 ◽  
Vol 37 (8) ◽  
pp. 1889-1890 ◽  
Author(s):  
Harold Hershenson ◽  
Sidney W. Benson
Keyword(s):  
Pressure Dependence ◽  
Butoxy Radical

Simple Test of Unimolecular Reaction Theory

1967 ◽  
Vol 46 (11) ◽  
pp. 4504-4508 ◽  
Author(s):  
Richard K. Lyon
Keyword(s):  
Unimolecular Reaction ◽  
Simple Test ◽  
Reaction Theory

A Combined Experimental and Theoretical Investigation of the Reactions of 3-Pentoxy Radicals: Reaction with O2 and Unimolecular Decomposition

2000 ◽  
Vol 214 (4) ◽  
Author(s):  
H. Hein ◽  
H. Somnitz ◽  
A. Hoffmann ◽  
R. Zellner
Keyword(s):  
Experimental Investigation ◽  
Theoretical Investigation ◽  
Unimolecular Reaction ◽  
Unimolecular Decomposition ◽  
Reaction Channels

The reactions of 3-pentoxy radicals with OIn addition to the experimental investigation, the unimolecular reaction channels of 3-pentoxy radicals were also analyzed by a combined

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