Multi-structural variational transition state theory. Kinetics of the 1,4-hydrogen shift isomerization of the pentyl radical with torsional anharmonicity

Yu, Tao; Zheng, Jingjing; Truhlar, Donald G.

doi:10.1039/c1sc00225b

Cited by 149 publications

(192 citation statements)

References 75 publications

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“…The lowest-energy saddle point usually has a larger Q S, ‡ k than any of the other transition state structures, especially at low temperature where the k k differ most significantly from unity. If we set P ¼ 1 in eqn(25), the MP-VTST/MT rate constant is reduced to the MS-VTST/MT rate constant27 …”

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confidence: 99%

Multi-path variational transition state theory for chemical reaction rates of complex polyatomic species: ethanol + OH reactions

2012

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Complex molecules often have many structures (conformations) of the reactants and the transition states, and these structures may be connected by coupled-mode torsions and pseudorotations; some but not all structures may have hydrogen bonds in the transition state or reagents. A quantitative theory of the reaction rates of complex molecules must take account of these structures, their coupled-mode nature, their qualitatively different character, and the possibility of merging reaction paths at high temperature. We have recently developed a coupled-mode theory called multi-structural variational transition state theory (MS-VTST) and an extension, called multi-path variational transition state theory (MP-VTST), that includes a treatment of the differences in the multi-dimensional tunneling paths and their contributions to the reaction rate. The MP-VTST method was presented for unimolecular reactions in the original paper and has now been extended to bimolecular reactions. The MS-VTST and MP-VTST formulations of variational transition state theory include multi-faceted configuration-space dividing surfaces to define the variational transition state. They occupy an intermediate position between single-conformation variational transition state theory (VTST), which has been used successfully for small molecules, and ensemble-averaged variational transition state theory (EA-VTST), which has been used successfully for enzyme kinetics. The theories are illustrated and compared here by application to three thermal rate constants for reactions of ethanol with hydroxyl radical--reactions with 4, 6, and 14 saddle points.

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confidence: 99%

Multi-path variational transition state theory for chemical reaction rates of complex polyatomic species: ethanol + OH reactions

2012

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“…In this case, much of the effort is devoted to describe as accurately as possible quantum mechanical effects on reaction coordinate motion, using multidimensional tunnelling corrections, and to account more accurately for recrossing effects. Recent developments of the VTST extends multistructural VTST [36] to incorporate multiple paths in the calculation of the tunnelling transmission coefficient and the variational effect: MP-VTST, [37] but at the expense of requiring substantial additional electronic structure information. Table 2 gives an overview of the capabilities of KiSThelP compared to a selection of programs among the most widely used in the field.…”

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confidence: 99%

KiSThelP: A program to predict thermodynamic properties and rate constants from quantum chemistry results^†

2013

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Kinetic and Statistical Thermodynamical Package (KiSThelP) is a cross-platform free open-source program developed to estimate molecular and reaction properties from electronic structure data. To date, three computational chemistry software formats are supported (Gaussian, GAMESS, and NWChem). Some key features are: gas-phase molecular thermodynamic properties (offering hindered rotor treatment), thermal equilibrium constants, transition state theory rate coefficients (transition state theory (TST), variational transition state theory (VTST)) including one-dimensional (1D) tunnelling effects (Wigner, and Eckart) and Rice-Ramsperger-Kassel-Marcus (RRKM) rate constants, for elementary reactions with welldefined barriers. KiSThelP is intended as a working tool both for the general public and also for more expert users. It provides graphical front-end capabilities designed to facilitate calculations and interpreting results. KiSThelP enables to change input data and simulation parameters directly through the graphical user interface and to visually probe how it affects results. Users can access results in the form of graphs and tables. The graphical tool offers customizing of 2D plots, exporting images and data files. These features make this program also well-suited to support and enhance students learning and can serve as a very attractive courseware, taking the teaching content directly from results in molecular and kinetic modelling.

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“…Within the context of MS-T, this ratio is usually referred to as the "F-factor," 22,23 which is given by…”

Section: Theoretical Approachmentioning

confidence: 99%

Computational Study of the Thermochemistry of N₂O₅ and the Kinetics of the Reaction N₂O₅ + H₂O → 2 HNO₃

Alecu

Marshall

2014

J. Phys. Chem. A

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The multistructural method for torsional anharmonicity (MS-T) is employed to compute anharmonic conformationally averaged partition functions which then serve as the basis for the calculation of thermochemical parameters for N 2 O 5 over the temperature range 0−3000 K, and thermal rate constants for the hydrolysis reaction N 2 O 5 + H 2 O → 2 HNO 3 over the temperature range 180−1800 K. The M06-2X hybrid meta-GGA density functional paired with the MG3S basis set is used to compute the properties of all stationary points and the energies, gradients, and Hessians of nonstationary points along the reaction path, with further energy refinement at stationary points obtained via single-point CCSD(T)-F12a/cc-pVTZ-F12 calculations including corrections for core−valence and scalar relativistic effects. The internal rotations in dinitrogen pentoxide are found to generate three structures (conformations) whose contributions are included in the partition function via the MS-T formalism, leading to a computed value for

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Multi-structural variational transition state theory. Kinetics of the 1,4-hydrogen shift isomerization of the pentyl radical with torsional anharmonicity

Cited by 149 publications

References 75 publications

Multi-path variational transition state theory for chemical reaction rates of complex polyatomic species: ethanol + OH reactions

Multi-path variational transition state theory for chemical reaction rates of complex polyatomic species: ethanol + OH reactions

KiSThelP: A program to predict thermodynamic properties and rate constants from quantum chemistry results^†

Computational Study of the Thermochemistry of N₂O₅ and the Kinetics of the Reaction N₂O₅ + H₂O → 2 HNO₃

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Multi-structural variational transition state theory. Kinetics of the 1,4-hydrogen shift isomerization of the pentyl radical with torsional anharmonicity

Cited by 149 publications

References 75 publications

Multi-path variational transition state theory for chemical reaction rates of complex polyatomic species: ethanol + OH reactions

Multi-path variational transition state theory for chemical reaction rates of complex polyatomic species: ethanol + OH reactions

KiSThelP: A program to predict thermodynamic properties and rate constants from quantum chemistry results†

Computational Study of the Thermochemistry of N2O5 and the Kinetics of the Reaction N2O5 + H2O → 2 HNO3

Contact Info

Product

Resources

About

KiSThelP: A program to predict thermodynamic properties and rate constants from quantum chemistry results^†

Computational Study of the Thermochemistry of N₂O₅ and the Kinetics of the Reaction N₂O₅ + H₂O → 2 HNO₃