Thermal decomposition of iso-propanol: First-principles prediction of total and product-branching rate constants

2002 ◽  
Vol 117 (24) ◽  
pp. 11188-11195 ◽  
Author(s):  
B. H. Bui ◽  
R. S. Zhu ◽  
M. C. Lin
Keyword(s):  
Thermal Decomposition ◽  
Rate Constants ◽  
First Principles ◽  
Product Branching

scholarly journals Influence of Multiple Conformations and Paths on Rate Constants and Product Branching Ratios. Thermal Decomposition of 1-Propanol Radicals

2018 ◽  
Vol 122 (21) ◽  
pp. 4790-4800 ◽  
Author(s):  
David Ferro-Costas ◽  
Emilio Martínez-Núñez ◽  
Jesús Rodríguez-Otero ◽  
Enrique Cabaleiro-Lago ◽  
Carlos M. Estévez ◽  
...  
Keyword(s):  
Thermal Decomposition ◽  
Rate Constants ◽  
Branching Ratios ◽  
Multiple Conformations ◽  
Product Branching

Substituent effects of rate constants for thermal [4π + 2π] cycloreversion of spiro-fused β-lactam oxadiazolines

1993 ◽  
Vol 71 (6) ◽  
pp. 907-911 ◽  
Author(s):  
Michel Zoghbi ◽  
John Warkentin
Keyword(s):  
Thermal Decomposition ◽  
Rate Constant ◽  
Rate Constants ◽  
Transition States ◽  
Substituent Effects ◽  
Ground States ◽  
Phenyl Substituent ◽  
First Order ◽  
Average Value ◽  
Carbonyl Ylide

Twelve Δ3-1,3,4-oxadiazolines in which C-2 is also C-4 of a β-lactam moiety (spiro-fused β-lactam oxadiazoline system) were thermolyzed as solutions in benzene. Substituents in the β-lactam portion affect the rate constant for thermal decomposition of the oxadiazolines to N2, acetone, and a β-lactam-4-ylidene. The total spread of first-order rate constants at 100 °C was 47-fold and the average value was 6.7 × 10−4 s−1. A phenyl substituent at N-1 or at C-3 was found to be rate enhancing, relative to methyl. At C-3, H and Cl were also rate enhancing, relative to methyl. The data are interpreted in terms of the differential effects of substituents on the stabilities of the ground states, and on the stabilities of corresponding transition states for concerted, suprafacial, [4π + 2π] cycloreversion. The first products, presumably formed irreversibly, are N2 and a carbonyl ylide. The latter subsequently fragments to form acetone (quantitative) and a β-lactam-4-ylidene.

Rate Constants and Product Branching Fractions for the Reactions of H3O+and NO+with C2−C12Alkanes

1998 ◽  
Vol 102 (45) ◽  
pp. 8881-8887 ◽  
Author(s):  
Susan T. Arnold ◽  
A. A. Viggiano ◽  
Robert A. Morris
Keyword(s):  
Rate Constants ◽  
Branching Fractions ◽  
Product Branching

scholarly journals First-principles calculations of anharmonic and deuteration effects on the photophysical properties of polyacenes and porphyrinoids

2020 ◽  
Vol 22 (39) ◽  
pp. 22314-22323 ◽  
Author(s):  
R. R. Valiev ◽  
R. T. Nasibullin ◽  
V. N. Cherepanov ◽  
G. V. Baryshnikov ◽  
D. Sundholm ◽  
...  
Keyword(s):  
Rate Constants ◽  
First Principles ◽  
Conversion Rate ◽  
Internal Conversion ◽  
Photophysical Properties ◽  
New Method ◽  
Lagrangian Multiplier ◽  
First Principles Calculations ◽  
Anharmonic Effects

A new method for calculating internal conversion rate constants (kIC), including anharmonic effects and using the Lagrangian multiplier technique, is proposed.

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