Cost-Effective Implementation of Multiconformer Transition State Theory for Peroxy Radical Hydrogen Shift Reactions

Kristian H. Møller, Rasmus V. Otkjaer, Noora Hyttinen, Theo Christian Kurten, Henrik G. Kjaergaard

Tutkimustuotos: ArtikkelijulkaisuArtikkeliTieteellinenvertaisarvioitu

Kuvaus

Based on a small test system, (R)-CH(OH)(OO center dot)CH2CHO, we have developed a cost-effective approach to the practical implementation of multiconformer transition state theory for peroxy radical hydrogen shift reactions at atmospherically relevant temperatures. While conformer searching is crucial for accurate reaction rates, an energy cutoff can be used to significantly reduce the computational cost with little loss of accuracy. For the reaction barrier, high-level calculations are needed, but the highest level of electronic structure theory is not necessary for the relative energy between conformers. Improving the approach to both transition state theory and electronic structure theory decreases the calculated reaction rate significantly, so low-level calculations can be used to rule out slow reactions. Further computational time can be saved by approximating the tunneling coefficients for each transition state by only that of the lowest-energy transition state. Finally, we test and validate our approach using higher-level theoretical values for our test system and existing experimental results for additional peroxy radical hydrogen shift reactions in three slightly larger systems.
Alkuperäiskielienglanti
LehtiJournal of Physical Chemistry A
Vuosikerta120
Numero51
Sivut10072-10087
Sivumäärä16
ISSN1089-5639
DOI - pysyväislinkit
TilaJulkaistu - 2016
OKM-julkaisutyyppiA1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä, vertaisarvioitu

Tieteenalat

  • 116 Kemia

Lainaa tätä

Møller, Kristian H. ; Otkjaer, Rasmus V. ; Hyttinen, Noora ; Kurten, Theo Christian ; Kjaergaard, Henrik G. / Cost-Effective Implementation of Multiconformer Transition State Theory for Peroxy Radical Hydrogen Shift Reactions. Julkaisussa: Journal of Physical Chemistry A. 2016 ; Vuosikerta 120, Nro 51. Sivut 10072-10087.
@article{4f1eb4250b7c4c1abeb43f5a8c175abc,
title = "Cost-Effective Implementation of Multiconformer Transition State Theory for Peroxy Radical Hydrogen Shift Reactions",
abstract = "Based on a small test system, (R)-CH(OH)(OO center dot)CH2CHO, we have developed a cost-effective approach to the practical implementation of multiconformer transition state theory for peroxy radical hydrogen shift reactions at atmospherically relevant temperatures. While conformer searching is crucial for accurate reaction rates, an energy cutoff can be used to significantly reduce the computational cost with little loss of accuracy. For the reaction barrier, high-level calculations are needed, but the highest level of electronic structure theory is not necessary for the relative energy between conformers. Improving the approach to both transition state theory and electronic structure theory decreases the calculated reaction rate significantly, so low-level calculations can be used to rule out slow reactions. Further computational time can be saved by approximating the tunneling coefficients for each transition state by only that of the lowest-energy transition state. Finally, we test and validate our approach using higher-level theoretical values for our test system and existing experimental results for additional peroxy radical hydrogen shift reactions in three slightly larger systems.",
keywords = "116 Chemical sciences",
author = "M{\o}ller, {Kristian H.} and Otkjaer, {Rasmus V.} and Noora Hyttinen and Kurten, {Theo Christian} and Kjaergaard, {Henrik G.}",
year = "2016",
doi = "10.1021/acs.jpca.6b09370",
language = "English",
volume = "120",
pages = "10072--10087",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "51",

}

Cost-Effective Implementation of Multiconformer Transition State Theory for Peroxy Radical Hydrogen Shift Reactions. / Møller, Kristian H.; Otkjaer, Rasmus V.; Hyttinen, Noora; Kurten, Theo Christian; Kjaergaard, Henrik G.

julkaisussa: Journal of Physical Chemistry A, Vuosikerta 120, Nro 51, 2016, s. 10072-10087.

Tutkimustuotos: ArtikkelijulkaisuArtikkeliTieteellinenvertaisarvioitu

TY - JOUR

T1 - Cost-Effective Implementation of Multiconformer Transition State Theory for Peroxy Radical Hydrogen Shift Reactions

AU - Møller, Kristian H.

AU - Otkjaer, Rasmus V.

AU - Hyttinen, Noora

AU - Kurten, Theo Christian

AU - Kjaergaard, Henrik G.

PY - 2016

Y1 - 2016

N2 - Based on a small test system, (R)-CH(OH)(OO center dot)CH2CHO, we have developed a cost-effective approach to the practical implementation of multiconformer transition state theory for peroxy radical hydrogen shift reactions at atmospherically relevant temperatures. While conformer searching is crucial for accurate reaction rates, an energy cutoff can be used to significantly reduce the computational cost with little loss of accuracy. For the reaction barrier, high-level calculations are needed, but the highest level of electronic structure theory is not necessary for the relative energy between conformers. Improving the approach to both transition state theory and electronic structure theory decreases the calculated reaction rate significantly, so low-level calculations can be used to rule out slow reactions. Further computational time can be saved by approximating the tunneling coefficients for each transition state by only that of the lowest-energy transition state. Finally, we test and validate our approach using higher-level theoretical values for our test system and existing experimental results for additional peroxy radical hydrogen shift reactions in three slightly larger systems.

AB - Based on a small test system, (R)-CH(OH)(OO center dot)CH2CHO, we have developed a cost-effective approach to the practical implementation of multiconformer transition state theory for peroxy radical hydrogen shift reactions at atmospherically relevant temperatures. While conformer searching is crucial for accurate reaction rates, an energy cutoff can be used to significantly reduce the computational cost with little loss of accuracy. For the reaction barrier, high-level calculations are needed, but the highest level of electronic structure theory is not necessary for the relative energy between conformers. Improving the approach to both transition state theory and electronic structure theory decreases the calculated reaction rate significantly, so low-level calculations can be used to rule out slow reactions. Further computational time can be saved by approximating the tunneling coefficients for each transition state by only that of the lowest-energy transition state. Finally, we test and validate our approach using higher-level theoretical values for our test system and existing experimental results for additional peroxy radical hydrogen shift reactions in three slightly larger systems.

KW - 116 Chemical sciences

U2 - 10.1021/acs.jpca.6b09370

DO - 10.1021/acs.jpca.6b09370

M3 - Article

VL - 120

SP - 10072

EP - 10087

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 51

ER -