التفاصيل البيبلوغرافية
| العنوان: |
Thermal and Vibrationally Activated Decomposition of the syn-CH 3 CHOO Criegee Intermediate |
| المؤلفون: |
Meenu Upadhyay (10290216), Markus Meuwly (1433455) |
| سنة النشر: |
2021 |
| المجموعة: |
Smithsonian Institution: Digital Repository |
| مصطلحات موضوعية: |
Biophysics, Biochemistry, Medicine, Pharmacology, Computational Biology, Biological Sciences not elsewhere classified, Chemical Sciences not elsewhere classified, Physical Sciences not elsewhere classified, nanosecond time scale, experimentally measured rate, 182 ± 66, vibrationally activated decomposition, thermally prepared reactants, experimentally reported yields, dissociation energy (<, actual rates depend, full reaction pathway, estimated thermal rate, choo criegee intermediate, oo , 3 , 3 , 2 , vhp eliminate oh, oh elimination rates, oh yields, oh elimination, vibrationally excited, reaction times, reactants influences |
| الوصف: |
The full reaction pathway between the syn -CH 3 CHOO Criegee Intermediate via vinyl hydroxyperoxide (VHP) to CH 2 COH+OH is followed for vibrationally excited and thermally prepared reactants. Reactivity along the entire pathway was characterized from an aggregate of more than 10 μs of reactive MD simulations using energy functions with accuracies at the Møller–Plesset second order level of theory. Reaction times for OH elimination are on the nanosecond time scale, and the energy dependence of the rates is consistent with experiments in the jet. The actual rates depend on the O–O dissociation energy ( D e OO = 31.5 kcal/mol at the MP2/aug-cc-pVTZ level or D e OO = 23.5 kcal/mol closer to earlier CASPT2 calculations). Also, the initial preparation of the reactants influences both the VHP formation/OH elimination rates and the OH yields. For most conditions with initial vibrational excitation 80% or more of syn -CH 3 CHOO progress to OH elimination on the 5 ns time scale. However, for internally cold conformational ensembles generated at low temperature (50 K) only 20% to 30% of VHP eliminate OH on the 5 ns time scale which increases to 55% to 67% depending on excitation energy from simulations on the 15 ns time scale. For thermal preparation of syn -CH 3 CHOO, which is relevant in the atmosphere, 35% of the trajectories lead to OH-elimination within 1 ns. This compares with experimentally reported yields of 24% to 64% in a collisional environment. The estimated thermal rate at 300 K is 10 3 s –1 , extrapolated from results at 500 to 900 K, is consistent with the experimentally measured rate of 182 ± 66 s –1 . |
| نوع الوثيقة: |
article in journal/newspaper |
| اللغة: |
unknown |
| العلاقة: |
https://figshare.com/articles/journal_contribution/Thermal_and_Vibrationally_Activated_Decomposition_of_the_syn-CH_sub_3_sub_CHOO_Criegee_Intermediate/17091594Test |
| DOI: |
10.1021/acsearthspacechem.1c00249.s001 |
| الإتاحة: |
https://doi.org/10.1021/acsearthspacechem.1c00249.s001Test |
| حقوق: |
CC BY-NC 4.0 |
| رقم الانضمام: |
edsbas.C7F0467 |
| قاعدة البيانات: |
BASE |
