Bypassing the multireference character of singlet molecular oxygen, part 1:1,4‐cyclo‐addition

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Standard

Bypassing the multireference character of singlet molecular oxygen, part 1:1,4‐cyclo‐addition. / Jespersen, Malte F.; Jørgensen, Solvejg; Johnson, Matthew S.; Mikkelsen, Kurt V.

I: International Journal of Quantum Chemistry, Bind 121, Nr. 6, e26523, 15.03.2021.

Publikation: Bidrag til tidsskriftTidsskriftartikelfagfællebedømt

Harvard

Jespersen, MF, Jørgensen, S, Johnson, MS & Mikkelsen, KV 2021, 'Bypassing the multireference character of singlet molecular oxygen, part 1:1,4‐cyclo‐addition', International Journal of Quantum Chemistry, bind 121, nr. 6, e26523. https://doi.org/10.1002/qua.26523

APA

Jespersen, M. F., Jørgensen, S., Johnson, M. S., & Mikkelsen, K. V. (2021). Bypassing the multireference character of singlet molecular oxygen, part 1:1,4‐cyclo‐addition. International Journal of Quantum Chemistry, 121(6), [e26523]. https://doi.org/10.1002/qua.26523

Vancouver

Jespersen MF, Jørgensen S, Johnson MS, Mikkelsen KV. Bypassing the multireference character of singlet molecular oxygen, part 1:1,4‐cyclo‐addition. International Journal of Quantum Chemistry. 2021 mar. 15;121(6). e26523. https://doi.org/10.1002/qua.26523

Author

Jespersen, Malte F. ; Jørgensen, Solvejg ; Johnson, Matthew S. ; Mikkelsen, Kurt V. / Bypassing the multireference character of singlet molecular oxygen, part 1:1,4‐cyclo‐addition. I: International Journal of Quantum Chemistry. 2021 ; Bind 121, Nr. 6.

Bibtex

@article{3755531403144354950d20cd9ccee679,
title = "Bypassing the multireference character of singlet molecular oxygen, part 1:1,4‐cyclo‐addition",
abstract = "Modeling reactions involving singlet molecular oxygen (O2 [1Δg]) is challenging because the degeneracy of the highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO and LUMO) orbitals of oxygen causes a significant multireference character. Within the limit that singlet-singlet near-degeneracy disappears in the transition state, it would be possible to bypass singlet oxygen's multireference character by simply adding the experimentally determined singlet/triplet splitting (22.5 kcal/mol) to the energy of the triplet ground state of molecular oxygen. This method is tested by calculating rate constants for the reactions of singlet molecular oxygen with furan, 2-methylfuran, 2,5-dimethylfuran, pyrrole, 2-methylpyrrole, 2,5-dimethylpyrrole, and cyclopentadiene using transition state theory. We find that the reaction rate coefficients are within a factor of 15 of experimentally determined rate constants, indicating an error in the barrier energy of roughly 3 kcal/mol. Furthermore, we find that energy refinement at the CCSD(T)-F12 level of theory is crucial to achieving accurate results. We conclude that, based on a comparison with an experiment, this approximation is valid to some degree and can be used for other systems involving the 1,4-cyclo-addition of singlet oxygen.",
author = "Jespersen, {Malte F.} and Solvejg J{\o}rgensen and Johnson, {Matthew S.} and Mikkelsen, {Kurt V.}",
year = "2021",
month = mar,
day = "15",
doi = "10.1002/qua.26523",
language = "English",
volume = "121",
journal = "International Journal of Quantum Chemistry",
issn = "0020-7608",
publisher = "JohnWiley & Sons, Inc.",
number = "6",

}

RIS

TY - JOUR

T1 - Bypassing the multireference character of singlet molecular oxygen, part 1:1,4‐cyclo‐addition

AU - Jespersen, Malte F.

AU - Jørgensen, Solvejg

AU - Johnson, Matthew S.

AU - Mikkelsen, Kurt V.

PY - 2021/3/15

Y1 - 2021/3/15

N2 - Modeling reactions involving singlet molecular oxygen (O2 [1Δg]) is challenging because the degeneracy of the highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO and LUMO) orbitals of oxygen causes a significant multireference character. Within the limit that singlet-singlet near-degeneracy disappears in the transition state, it would be possible to bypass singlet oxygen's multireference character by simply adding the experimentally determined singlet/triplet splitting (22.5 kcal/mol) to the energy of the triplet ground state of molecular oxygen. This method is tested by calculating rate constants for the reactions of singlet molecular oxygen with furan, 2-methylfuran, 2,5-dimethylfuran, pyrrole, 2-methylpyrrole, 2,5-dimethylpyrrole, and cyclopentadiene using transition state theory. We find that the reaction rate coefficients are within a factor of 15 of experimentally determined rate constants, indicating an error in the barrier energy of roughly 3 kcal/mol. Furthermore, we find that energy refinement at the CCSD(T)-F12 level of theory is crucial to achieving accurate results. We conclude that, based on a comparison with an experiment, this approximation is valid to some degree and can be used for other systems involving the 1,4-cyclo-addition of singlet oxygen.

AB - Modeling reactions involving singlet molecular oxygen (O2 [1Δg]) is challenging because the degeneracy of the highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO and LUMO) orbitals of oxygen causes a significant multireference character. Within the limit that singlet-singlet near-degeneracy disappears in the transition state, it would be possible to bypass singlet oxygen's multireference character by simply adding the experimentally determined singlet/triplet splitting (22.5 kcal/mol) to the energy of the triplet ground state of molecular oxygen. This method is tested by calculating rate constants for the reactions of singlet molecular oxygen with furan, 2-methylfuran, 2,5-dimethylfuran, pyrrole, 2-methylpyrrole, 2,5-dimethylpyrrole, and cyclopentadiene using transition state theory. We find that the reaction rate coefficients are within a factor of 15 of experimentally determined rate constants, indicating an error in the barrier energy of roughly 3 kcal/mol. Furthermore, we find that energy refinement at the CCSD(T)-F12 level of theory is crucial to achieving accurate results. We conclude that, based on a comparison with an experiment, this approximation is valid to some degree and can be used for other systems involving the 1,4-cyclo-addition of singlet oxygen.

U2 - 10.1002/qua.26523

DO - 10.1002/qua.26523

M3 - Journal article

VL - 121

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

SN - 0020-7608

IS - 6

M1 - e26523

ER -

ID: 257919915