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

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.

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Computational Kinetics by Variational Transition-State Theory with Semiclassical Multidimensional Tunneling: Direct Dynamics Rate Constants for the Abstraction of H from CH3OH by Triplet Oxygen Atoms

The Journal of Physical Chemistry A ◽

10.1021/acs.jpca.6b10600 ◽

2017 ◽

Vol 121 (8) ◽

pp. 1693-1707 ◽

Cited By ~ 8

Author(s):

Rubén Meana-Pañeda ◽

Xuefei Xu ◽

He Ma ◽

Donald G. Truhlar

Keyword(s):

Transition State ◽

Rate Constants ◽

Transition State Theory ◽

State Theory ◽

Variational Transition State Theory ◽

Direct Dynamics ◽

Multidimensional Tunneling ◽

Variational Transition State ◽

Oxygen Atoms

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Test of variational transition state theory and the least‐action approximation for multidimensional tunneling probabilities against accurate quantal rate constants for a collinear reaction involving tunneling into an excited state

The Journal of Chemical Physics ◽

10.1063/1.449318 ◽

1985 ◽

Vol 83 (5) ◽

pp. 2252-2258 ◽

Cited By ~ 63

Author(s):

Bruce C. Garrett ◽

Najib Abusalbi ◽

Donald J. Kouri ◽

Donald G. Truhlar

Keyword(s):

Excited State ◽

Transition State ◽

Rate Constants ◽

Transition State Theory ◽

State Theory ◽

Variational Transition State Theory ◽

Least Action ◽

Multidimensional Tunneling ◽

Variational Transition State

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Theoretical Study on the Reaction of Et3GeCH=CH2 with Et3SiOH

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.549.301 ◽

2012 ◽

Vol 549 ◽

pp. 301-304

Author(s):

Xin Cheng Chen ◽

Xiao Yun Han ◽

Wan Yong Ma ◽

Li Gang Gai

Keyword(s):

Quantum Chemistry ◽

Transition State ◽

Rate Constants ◽

Transition State Theory ◽

Theoretical Study ◽

State Theory ◽

Arrhenius Behavior ◽

Variational Transition State Theory ◽

Temperature Range ◽

Variational Transition State

The reaction of Et3GeCH=CH2 + Et3SiOH → Et3SiO–Ge–Et3 + CH2=CH2 has been studied using quantum chemistry methods. Geometries of reactants, transition states, and products have been optimized respectively at the b3lyp/6-311+g(2d,2p) level. The rate constants were evaluated using canonical variational transition state theory (CVT) and canonical variational transition state theory with small-curvaturetunneling contributions (CVT/SCT) over the temperature range of 200-3500K. The CVT/SCT rate constants exhibit typical non-Arrhenius behavior, and a three-parameter rate-temperature formula has been fitted as follows: k(T)=1.43×10-38T 5.41exp(-13200/T) (in units of cm3 molecule-1s-1).

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Barrierless association of CF2and dissociation of C2F4by variational transition-state theory and system-specific quantum Rice–Ramsperger–Kassel theory

Proceedings of the National Academy of Sciences ◽

10.1073/pnas.1616208113 ◽

2016 ◽

Vol 113 (48) ◽

pp. 13606-13611 ◽

Cited By ~ 14

Author(s):

Junwei Lucas Bao ◽

Xin Zhang ◽

Donald G. Truhlar

Keyword(s):

Transition State ◽

Rate Constants ◽

Transition State Theory ◽

Dissociation Rate ◽

State Theory ◽

Variational Transition State Theory ◽

Exchange Correlation ◽

Direct Dynamics ◽

Specific Quantum ◽

Variational Transition State

Bond dissociation is a fundamental chemical reaction, and the first principles modeling of the kinetics of dissociation reactions with a monotonically increasing potential energy along the dissociation coordinate presents a challenge not only for modern electronic structure methods but also for kinetics theory. In this work, we use multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) to compute the high-pressure limit dissociation rate constant of tetrafluoroethylene (C2F4), in which the potential energies are computed by direct dynamics with the M08-HX exchange correlation functional. To treat the pressure dependence of the unimolecular rate constants, we use the recently developed system-specific quantum Rice–Ramsperger–Kassel theory. The calculations are carried out by direct dynamics using an exchange correlation functional validated against calculations that go beyond coupled-cluster theory with single, double, and triple excitations. Our computed dissociation rate constants agree well with the recent experimental measurements.

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Calculating rate constants with updated Hessians using variational transition state theory with multidimensional tunneling

Journal of Computational Chemistry ◽

10.1002/jcc.20705 ◽

2007 ◽

Vol 28 (11) ◽

pp. 1809-1816 ◽

Cited By ~ 1

Author(s):

Yao-Yuan Chuang

Keyword(s):

Transition State ◽

Rate Constants ◽

Transition State Theory ◽

State Theory ◽

Variational Transition State Theory ◽

Multidimensional Tunneling ◽

Variational Transition State

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Silane-initiated nucleation in chemically active plasmas: validation of density functionals, mechanisms, and pressure-dependent variational transition state calculations

Physical Chemistry Chemical Physics ◽

10.1039/c6cp00816j ◽

2016 ◽

Vol 18 (15) ◽

pp. 10097-10108 ◽

Cited By ~ 16

Author(s):

Junwei Lucas Bao ◽

Donald G. Truhlar

Keyword(s):

Transition State ◽

Rate Constants ◽

Transition State Theory ◽

State Theory ◽

Density Functionals ◽

Variational Transition State Theory ◽

Dependent Rate ◽

Nanodusty Plasmas ◽

Specific Quantum ◽

Variational Transition State

Pressure-dependent rate constants for nucleation in nanodusty plasmas are calculated by variational transition state theory with system-specific quantum RRK theory.

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