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|---|---|---|---|
| 001 | 667867 | ||
| 005 | 20231030042129.0 | ||
| 035 | _a(RuTPU)RU\TPU\network\39078 | ||
| 035 | _aRU\TPU\network\22319 | ||
| 090 | _a667867 | ||
| 100 | _a20220511a2021 k y0engy50 ba | ||
| 101 | 0 | _aeng | |
| 102 | _aUS | ||
| 135 | _adrcn ---uucaa | ||
| 181 | 0 | _ai | |
| 182 | 0 | _ab | |
| 200 | 1 |
_aComputational Investigation of the Formation of Peroxide (ROOR) Accretion Products in the OH- and NO3-Initiated Oxidation of α-Pinene _fH. Galib, R. R. Valiev, S. Vili-Taneli, T. Kurten |
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| 203 |
_aText _celectronic |
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| 300 | _aTitle screen | ||
| 320 | _a[References: 43 tit.] | ||
| 330 | _aThe formation of accretion products (“dimers”) from recombination reactions of peroxyl radicals (RO2) is a key step in the gas-phase generation of low-volatility vapors, leading to atmospheric aerosol particles. We have recently demonstrated that this recombination reaction very likely proceeds via an intermediate complex of two alkoxy radicals (RO···OR′) and that the accretion product pathway involves an intersystem crossing (ISC) of this complex from the triplet to the singlet surface. However, ISC rates have hitherto not been computed for large and chemically complex RO···OR′ systems actually relevant to atmospheric aerosol formation. Here, we carry out systematic conformational sampling and ISC rate calculations on 3(RO···OR′) clusters formed in the recombination reactions of different diastereomers of the first-generation peroxyl radicals originating in both OH- and NO3-initiated reactions of α-pinene, a key biogenic hydrocarbon for atmospheric aerosol formation. While we find large differences between the ISC rates of different diastereomer pairs, all systems have ISC rates of at least 106 s-1, and many have rates exceeding 1010 s-1. Especially the latter value demonstrates that accretion product formation via the suggested pathway is a competitive process also for α-pinene-derived RO2 and likely explains the experimentally observed gas-phase formation of C20 compounds in α-pinene oxidation. | ||
| 333 | _aРежим доступа: по договору с организацией-держателем ресурса | ||
| 461 | _tJournal of Physical Chemistry A | ||
| 463 |
_tVol. 125, iss. 50 _v[P. 10632-10639] _d2021 |
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| 610 | 1 | _aэлектронный ресурс | |
| 610 | 1 | _aтруды учёных ТПУ | |
| 701 | 1 |
_aGalib _bH. _gHasan |
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| 701 | 1 |
_aValiev _bR. R. _cchemist _cAssistant of Tomsk Polytechnic University _f1983- _gRashid Rinatovich _2stltpush _3(RuTPU)RU\TPU\pers\34114 |
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| 701 | 1 |
_aVili-Taneli _bS. _gSalo |
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| 701 | 1 |
_aKurten _bT. _gTheo |
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| 801 | 2 |
_aRU _b63413507 _c20220511 _gRCR |
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| 856 | 4 | _uhttps://doi.org/10.1021/acs.jpca.1c08969 | |
| 942 | _cCF | ||