Kinetic parameters for the reaction of hydroxyl radical with CH3OCH2F (HFE-161) in the temperature range of 200-400 K: Transition state theory and Ab initio calculations

2011 ◽  
Vol 112 (4) ◽  
pp. 1066-1077 ◽  
Author(s):  
Veerabhadrarao Kaliginedi ◽  
Mohamad Akbar Ali ◽  
B. Rajakumar
Keyword(s):  
Transition State ◽  
Hydroxyl Radical ◽  
Ab Initio Calculations ◽  
Ab Initio ◽  
Kinetic Parameters ◽  
Transition State Theory ◽  
State Theory ◽  
Temperature Range

Quantum mechanical tunnelling in the processes D + H2 → DH + H and CH4 + H → CH3 + H2. Eckart's tunnelling corrections for rate constants given by ab initio calculations

1979 ◽  
Vol 44 (12) ◽  
pp. 3452-3457 ◽  
Author(s):  
Petr Čársky
Keyword(s):  
Transition State ◽  
Ab Initio Calculations ◽  
Ab Initio ◽  
Rate Constants ◽  
Transition State Theory ◽  
State Theory ◽  
Quantum Mechanical ◽  
Rate Data ◽  
Dimensional Approach ◽  
One Dimensional

Results of the best reported ab initio calculations are used to evaluate the rate constants of the title processes by means of the transition state theory. The computed rate constants are corrected for the quantum mechanical tunnelling by the Eckart's one-dimensional approach and comparison is made with experimental rate data

Recombination of methyl radicals: ab initio potential and transition-state theory calculations

1989 ◽  
Vol 93 (12) ◽  
pp. 4772-4779 ◽  
Author(s):  
Katherine Valenta Darvesh ◽  
Russell J. Boyd ◽  
Philip D. Pacey
Keyword(s):  
Transition State ◽  
Ab Initio ◽  
Transition State Theory ◽  
State Theory ◽  
Methyl Radicals

scholarly journals Advances in Automated Transition State Theory Calculations: Improvements on the AutoTST Framework

2020 ◽  
Author(s):  
Nathan Harms ◽  
Carl Underkoffler ◽  
Richard West
Keyword(s):  
Transition State ◽  
Kinetic Parameters ◽  
Transition State Theory ◽  
Vibrational Analysis ◽  
Chemical Kinetic ◽  
State Theory ◽  
Combustion Chemistry ◽  
Transition State Geometry ◽  
Substantial Progress ◽  
Symmetry Number

<div>Kinetic modeling of combustion chemistry has made substantial progress in recent years with the development of increasingly detailed models. However, many of the chemical kinetic parameters utilized in detailed models are estimated, often inaccurately. To help replace rate estimates with more accurate calculations, we have developed AutoTST, an automated Transition State Theory rate calculator. This work describes improvements to AutoTST, including: a systematic conformer search to find an ensemble of low energy conformers, vibrational analysis to validate transition state geometries, more accurate symmetry number calculations, and a hindered rotor treatment when deriving kinetics. These improvements resulted in location of transition state geometry for 93% of cases and generation of kinetic parameters for 74% of cases. Newly calculated parameters agree well with benchmark calculations and perform well when used to replace estimated parameters in a detailed kinetic model of methanol combustion.</div>

scholarly journals Advances in Automated Transition State Theory Calculations: Improvements on the AutoTST Framework

2020 ◽  
Author(s):  
Nathan Harms ◽  
Carl Underkoffler ◽  
Richard West
Keyword(s):  
Transition State ◽  
Kinetic Parameters ◽  
Transition State Theory ◽  
Vibrational Analysis ◽  
Chemical Kinetic ◽  
State Theory ◽  
Combustion Chemistry ◽  
Transition State Geometry ◽  
Substantial Progress ◽  
Symmetry Number

<div>Kinetic modeling of combustion chemistry has made substantial progress in recent years with the development of increasingly detailed models. However, many of the chemical kinetic parameters utilized in detailed models are estimated, often inaccurately. To help replace rate estimates with more accurate calculations, we have developed AutoTST, an automated Transition State Theory rate calculator. This work describes improvements to AutoTST, including: a systematic conformer search to find an ensemble of low energy conformers, vibrational analysis to validate transition state geometries, more accurate symmetry number calculations, and a hindered rotor treatment when deriving kinetics. These improvements resulted in location of transition state geometry for 93% of cases and generation of kinetic parameters for 74% of cases. Newly calculated parameters agree well with benchmark calculations and perform well when used to replace estimated parameters in a detailed kinetic model of methanol combustion.</div>

scholarly journals Predicting pressure-dependent unimolecular rate constants using variational transition state theory with multidimensional tunneling combined with system-specific quantum RRK theory: a definitive test for fluoroform dissociation

2016 ◽  
Vol 18 (25) ◽  
pp. 16659-16670 ◽  
Author(s):  
Junwei Lucas Bao ◽  
Xin Zhang ◽  
Donald G. Truhlar
Keyword(s):  
Experimental Data ◽  
Transition State ◽  
Rate Constants ◽  
Transition State Theory ◽  
State Theory ◽  
Variational Transition State Theory ◽  
Temperature Range ◽  
Multidimensional Tunneling ◽  
Specific Quantum ◽  
Wide Pressure

We show that rate constants for dissociation of fluoroform computed by VTST/SS-QRRK agree excellently with definitive experimental data over a wide pressure and temperature range.

Sign in / Sign up

Export Citation Format

Share Document