# The role of the transition state in polyatomic reactions: Initial state-selected reaction probabilities of the H + CH4 -> H-2 + CH3 reaction

Welsch R, Manthe U (2014) *The Journal of Chemical Physics* 141(17).

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Full-dimensional calculations of initial state-selected reaction probabilities on an accurate ab initio potential energy surface (PES) have been communicated recently [R. Welsch and U. Manthe, J. Chem. Phys. 141, 051102 (2014)]. These calculations use the quantum transition state concept, the multi-layer multi-configurational time-dependent Hartree approach, and graphics processing units to speed up the potential evaluation. Here further results of these calculations and an extended analysis are presented. State-selected reaction probabilities are given for many initial ro-vibrational states. The role of the vibrational states of the activated complex is analyzed in detail. It is found that rotationally cold methane mainly reacts via the ground state of the activated complex while rotationally excited methane mostly reacts via H-H-CH3-bending excited states of the activated complex. Analyzing the different contributions to the reactivity of the vibrationally states of methane, a complex pattern is found. Comparison with initial state-selected reaction probabilities computed on the semi-empirical Jordan-Gilbert PES reveals the dependence of the results on the specific PES. (C) 2014 AIP Publishing LLC.

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Welsch R, Manthe U. The role of the transition state in polyatomic reactions: Initial state-selected reaction probabilities of the H + CH4 -> H-2 + CH3 reaction.

*The Journal of Chemical Physics*. 2014;141(17).Welsch, R., & Manthe, U. (2014). The role of the transition state in polyatomic reactions: Initial state-selected reaction probabilities of the H + CH4 -> H-2 + CH3 reaction.

*The Journal of Chemical Physics*,*141*(17). doi:10.1063/1.4900735Welsch, R., and Manthe, U. (2014). The role of the transition state in polyatomic reactions: Initial state-selected reaction probabilities of the H + CH4 -> H-2 + CH3 reaction.

*The Journal of Chemical Physics*141.Welsch, R., & Manthe, U., 2014. The role of the transition state in polyatomic reactions: Initial state-selected reaction probabilities of the H + CH4 -> H-2 + CH3 reaction.

*The Journal of Chemical Physics*, 141(17). R. Welsch and U. Manthe, “The role of the transition state in polyatomic reactions: Initial state-selected reaction probabilities of the H + CH4 -> H-2 + CH3 reaction”,

*The Journal of Chemical Physics*, vol. 141, 2014. Welsch, R., Manthe, U.: The role of the transition state in polyatomic reactions: Initial state-selected reaction probabilities of the H + CH4 -> H-2 + CH3 reaction. The Journal of Chemical Physics. 141, (2014).

Welsch, Ralph, and Manthe, Uwe. “The role of the transition state in polyatomic reactions: Initial state-selected reaction probabilities of the H + CH4 -> H-2 + CH3 reaction”.

*The Journal of Chemical Physics*141.17 (2014).
This data publication is cited in the following publications:

This publication cites the following data publications:

### 15 Citations in Europe PMC

Data provided by Europe PubMed Central.

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Wang Y, Li Y, Wang D.,

PMID: 28071762

Wang Y, Li Y, Wang D.,

*Sci Rep*7(), 2017PMID: 28071762

On the multi-layer multi-configurational time-dependent Hartree approach for bosons and fermions.

Manthe U, Weike T.,

PMID: 28201897

Manthe U, Weike T.,

*J Chem Phys*146(6), 2017PMID: 28201897

A transition-state based rotational sudden (TSRS) approximation for polyatomic reactive scattering.

Zhao B, Manthe U.,

PMID: 29031274

Zhao B, Manthe U.,

*J Chem Phys*147(14), 2017PMID: 29031274

Recent advances in quantum scattering calculations on polyatomic bimolecular reactions.

Fu B, Shan X, Zhang DH, Clary DC.,

PMID: 29143835

Fu B, Shan X, Zhang DH, Clary DC.,

*Chem Soc Rev*46(24), 2017PMID: 29143835

Communication: Reactivity borrowing in the mode selective chemistry of H + CHD3 → H2 + CD3.

Ellerbrock R, Manthe U.,

PMID: 29289128

Ellerbrock R, Manthe U.,

*J Chem Phys*147(24), 2017PMID: 29289128

A reactant-coordinate-based wave packet method for full-dimensional state-to-state quantum dynamics of tetra-atomic reactions: Application to both the abstraction and exchange channels in the H + H2O reaction.

Zhao B, Sun Z, Guo H.,

PMID: 26874479

Zhao B, Sun Z, Guo H.,

*J Chem Phys*144(6), 2016PMID: 26874479

Recent Advances in Quantum Dynamics of Bimolecular Reactions.

Zhang DH, Guo H.,

PMID: 26980305

Zhang DH, Guo H.,

*Annu Rev Phys Chem*67(), 2016PMID: 26980305

Communication: Mode specific quantum dynamics of the F + CHD3 → HF + CD3 reaction.

Qi J, Song H, Yang M, Palma J, Manthe U, Guo H.,

PMID: 27155615

Qi J, Song H, Yang M, Palma J, Manthe U, Guo H.,

*J Chem Phys*144(17), 2016PMID: 27155615

S-matrix decomposition, natural reaction channels, and the quantum transition state approach to reactive scattering.

Manthe U, Ellerbrock R.,

PMID: 27250291

Manthe U, Ellerbrock R.,

*J Chem Phys*144(20), 2016PMID: 27250291

Rate constants of chemical reactions from semiclassical transition state theory in full and one dimension.

Greene SM, Shan X, Clary DC.,

PMID: 27369506

Greene SM, Shan X, Clary DC.,

*J Chem Phys*144(24), 2016PMID: 27369506

Full-dimensional and reduced-dimensional calculations of initial state-selected reaction probabilities studying the H + CH4 → H2 + CH3 reaction on a neural network PES.

Welsch R, Manthe U.,

PMID: 25681908

Welsch R, Manthe U.,

*J Chem Phys*142(6), 2015PMID: 25681908

A seven-degree-of-freedom, time-dependent quantum dynamics study on the energy efficiency in surmounting the central energy barrier of the OH + CH3 → O + CH4 reaction.

Yan P, Wang Y, Li Y, Wang D.,

PMID: 25933760

Yan P, Wang Y, Li Y, Wang D.,

*J Chem Phys*142(16), 2015PMID: 25933760

A permutationally invariant full-dimensional ab initio potential energy surface for the abstraction and exchange channels of the H + CH4 system.

Li J, Chen J, Zhao Z, Xie D, Zhang DH, Guo H.,

PMID: 26026442

Li J, Chen J, Zhao Z, Xie D, Zhang DH, Guo H.,

*J Chem Phys*142(20), 2015PMID: 26026442

The multi-configurational time-dependent Hartree approach revisited.

Manthe U.,

PMID: 26133412

Manthe U.,

*J Chem Phys*142(24), 2015PMID: 26133412

Mode specific dynamics of the H2 + CH3 → H + CH4 reaction studied using quasi-classical trajectory and eight-dimensional quantum dynamics methods.

Wang Y, Li J, Chen L, Lu Y, Yang M, Guo H.,

PMID: 26493907

Wang Y, Li J, Chen L, Lu Y, Yang M, Guo H.,

*J Chem Phys*143(15), 2015PMID: 26493907

### 101 References

Data provided by Europe PubMed Central.

Towards accurate ab initio predictions of the vibrational spectrum of methane.

Schwenke DW.,

PMID: 11991499

Schwenke DW.,

*Spectrochim Acta A Mol Biomol Spectrosc*58(4), 2002PMID: 11991499

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