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Spin-Forbidden Channels in Reactions of Unsaturated Hydrocarbons with O(3P)

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Spin-Forbidden Channels in Reactions of Unsaturated Hydrocarbons with O(3P). / Pokhilko, Pavel; Shannon, Robin; Glowacki, David; Wang, Hai; Krylov, Anna I.

In: Journal of Physical Chemistry A, Vol. 123, No. 2, 17.01.2019, p. 482-491.

Research output: Contribution to journalArticle

Harvard

Pokhilko, P, Shannon, R, Glowacki, D, Wang, H & Krylov, AI 2019, 'Spin-Forbidden Channels in Reactions of Unsaturated Hydrocarbons with O(3P)', Journal of Physical Chemistry A, vol. 123, no. 2, pp. 482-491. https://doi.org/10.1021/acs.jpca.8b10225

APA

Pokhilko, P., Shannon, R., Glowacki, D., Wang, H., & Krylov, A. I. (2019). Spin-Forbidden Channels in Reactions of Unsaturated Hydrocarbons with O(3P). Journal of Physical Chemistry A, 123(2), 482-491. https://doi.org/10.1021/acs.jpca.8b10225

Vancouver

Pokhilko P, Shannon R, Glowacki D, Wang H, Krylov AI. Spin-Forbidden Channels in Reactions of Unsaturated Hydrocarbons with O(3P). Journal of Physical Chemistry A. 2019 Jan 17;123(2):482-491. https://doi.org/10.1021/acs.jpca.8b10225

Author

Pokhilko, Pavel ; Shannon, Robin ; Glowacki, David ; Wang, Hai ; Krylov, Anna I. / Spin-Forbidden Channels in Reactions of Unsaturated Hydrocarbons with O(3P). In: Journal of Physical Chemistry A. 2019 ; Vol. 123, No. 2. pp. 482-491.

Bibtex

@article{296609db08bb4437bf606236ab1ff961,
title = "Spin-Forbidden Channels in Reactions of Unsaturated Hydrocarbons with O(3P)",
abstract = "The electronic structure of four prototypical Cvetanović diradicals, species derived by addition of O( 3 P) to unsaturated compounds, is investigated by high-level electronic structure calculations and kinetics modeling. The main focus of this study is on the electronic factors controlling the rate of intersystem crossing (ISC): minimal energy crossing points (MECPs) and spin-orbit couplings (SOCs). The calculations illuminate significant differences in the electronic structure of ethene- and ethyne-derived compounds and explain the effect of methylation. The computed MECP heights and SOCs reveal different mechanisms of ISC in ethene- and ethyne-derived species, thus explaining variations in the observed branching ratios between singlet and triplet products and a puzzling effect of methyl substitution. In the ethene- and propene-derived species, the MECP is very low and the rate is controlled by variations of SOC, whereas in the ethyne- and propyne-derived species the MECP is high and the changes in the ISC rate due to methyl substitutions are driven by the variations of MECP heights.",
author = "Pavel Pokhilko and Robin Shannon and David Glowacki and Hai Wang and Krylov, {Anna I.}",
year = "2019",
month = "1",
day = "17",
doi = "10.1021/acs.jpca.8b10225",
language = "English",
volume = "123",
pages = "482--491",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "2",

}

RIS - suitable for import to EndNote

TY - JOUR

T1 - Spin-Forbidden Channels in Reactions of Unsaturated Hydrocarbons with O(3P)

AU - Pokhilko, Pavel

AU - Shannon, Robin

AU - Glowacki, David

AU - Wang, Hai

AU - Krylov, Anna I.

PY - 2019/1/17

Y1 - 2019/1/17

N2 - The electronic structure of four prototypical Cvetanović diradicals, species derived by addition of O( 3 P) to unsaturated compounds, is investigated by high-level electronic structure calculations and kinetics modeling. The main focus of this study is on the electronic factors controlling the rate of intersystem crossing (ISC): minimal energy crossing points (MECPs) and spin-orbit couplings (SOCs). The calculations illuminate significant differences in the electronic structure of ethene- and ethyne-derived compounds and explain the effect of methylation. The computed MECP heights and SOCs reveal different mechanisms of ISC in ethene- and ethyne-derived species, thus explaining variations in the observed branching ratios between singlet and triplet products and a puzzling effect of methyl substitution. In the ethene- and propene-derived species, the MECP is very low and the rate is controlled by variations of SOC, whereas in the ethyne- and propyne-derived species the MECP is high and the changes in the ISC rate due to methyl substitutions are driven by the variations of MECP heights.

AB - The electronic structure of four prototypical Cvetanović diradicals, species derived by addition of O( 3 P) to unsaturated compounds, is investigated by high-level electronic structure calculations and kinetics modeling. The main focus of this study is on the electronic factors controlling the rate of intersystem crossing (ISC): minimal energy crossing points (MECPs) and spin-orbit couplings (SOCs). The calculations illuminate significant differences in the electronic structure of ethene- and ethyne-derived compounds and explain the effect of methylation. The computed MECP heights and SOCs reveal different mechanisms of ISC in ethene- and ethyne-derived species, thus explaining variations in the observed branching ratios between singlet and triplet products and a puzzling effect of methyl substitution. In the ethene- and propene-derived species, the MECP is very low and the rate is controlled by variations of SOC, whereas in the ethyne- and propyne-derived species the MECP is high and the changes in the ISC rate due to methyl substitutions are driven by the variations of MECP heights.

UR - http://www.scopus.com/inward/record.url?scp=85060167282&partnerID=8YFLogxK

U2 - 10.1021/acs.jpca.8b10225

DO - 10.1021/acs.jpca.8b10225

M3 - Article

VL - 123

SP - 482

EP - 491

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 2

ER -