Reaction Dynamics of O(P-3) + Propyne: I. Primary Products, Branching Ratios, and Role of Intersystem Crossing from Crossed Molecular Beam Experiments

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989100%3A27200%2F16%3A86099685" target="_blank" >RIV/61989100:27200/16:86099685 - isvavai.cz</a>

Result on the web

<a href="http://dx.doi.org/10.1021/acs.jpca.6b01563" target="_blank" >http://dx.doi.org/10.1021/acs.jpca.6b01563</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpca.6b01563" target="_blank" >10.1021/acs.jpca.6b01563</a>

Result language

angličtina

Original language name

Reaction Dynamics of O(P-3) + Propyne: I. Primary Products, Branching Ratios, and Role of Intersystem Crossing from Crossed Molecular Beam Experiments

Original language description

We performed synergic experimental/theoretical studies on the mechanism of the O(P-3) + propyne reaction by combining crossed molecular beams experiments with mass-spectrometric detection and time-of-flight analysis at 9.2 kcal/mol collision energy (E-c) with ab initio electronic structure calculations at a high level of theory of the relevant triplet and singlet potential energy surfaces (PESs) and statistical calculations of branching ratios (BRs) taking into account intersystem crossing (ISC). In this paper (I) we report the results of the experimental investigation, while the accompanying paper (II) shows results of the theoretical investigation with comparison to experimental results. By exploiting soft electron ionization detection to suppress/mitigate the effects of the dissociative ionization of reactants, products, and background gases, product angular and velocity distributions at different charge-to-mass ratios were measured. From the laboratory data angular and translational energy distributions in the center-of-mass system were obtained for the five competing most important product channels, and product BRs were derived. The reactive interaction of O(P-3) with propyne under single collision conditions is mainly leading to the rupture of the three-carbon atom chain, with production of the radical products methylketenyl + atomic hydrogen (BR = 0.04), methyl + ketenyl (BR = 0.10), and vinyl + formyl (BR = 0.11) and the molecular products ethylidene/ethylene + carbon monoxide (BR = 0.74) and propandienal + molecular hydrogen (BR = 0.01). Because some of the products can only be formed via ISC from the entrance triplet to the low-lying singlet PES, we infer from their BRs an amount of ISC larger than 80%. This value is dramatically large when compared to the negligible ISC reported for the O(P-3) reaction with the simplest alkyne, acetylene.

Czech name

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Czech description

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Type

J_x - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

CEP classification

CF - Physical chemistry and theoretical chemistry

OECD FORD branch

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Project

<a href="/en/project/LD11012" target="_blank" >LD11012: Combined models of chemical kinetics and fluid dynamics for simulation of cleaner combustion processes</a><br>

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2016

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

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Volume of the periodical

120

Issue of the periodical within the volume

27

Country of publishing house

US - UNITED STATES

Number of pages

16

Pages from-to

4603-4618

UT code for WoS article

000379988900003

EID of the result in the Scopus database

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