On the Mechanism of Soot Nucleation. III. The Fate and Facility of the E-Bridge

Frenklach, Michael; Semenikhin, Alexander S.; Mebel, Alexander M.

doi:10.1021/acs.jpca.1c04936

Title: On the Mechanism of Soot Nucleation. III. The Fate and Facility of the E-Bridge

Journal Article · 02 August 2021 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI: https://doi.org/10.1021/acs.jpca.1c04936 · OSTI ID:1843963

^[1]; Semenikhin, Alexander S. ^[2];

^[3]

Univ. of California, Berkeley, CA (United States); Florida International University
Samara National Research Univ. (Russia)
Florida International Univ. (FIU), Miami, FL (United States)

Rotationally-excited dimerization of aromatic moieties is a mechanism proposed recently to explain the initial steps of soot particle inception in combustion and pyrolysis of hydrocarbons. The product of such dimerization, termed E-bridge, is an angled molecular structure composed of two aromatic rings sharing a common bond. The present study explores the immediate fate of the E-bridge. The performed theoretical analysis indicates that abstraction of a bridge H atom by a gaseous H leads to a rapid transformation of the angled to planar structure. The implications of this result is that the collisionally-activated E-bridge formation followed by its flattening effectively increases the size of “planar” aromatic precursors by combining two aromatic moieties with essentially collisional rates, instead of a slower “atom-by-atom” buildup. The faster growth speeds up PAH reaching a size when physical dimerization takes over. Furthermore, the dimerization can be further assisted by the biradicaloid valence structure of the flattened E-bridge.

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Research Organization:: Florida International Univ. (FIU), Miami, FL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-04ER15570

OSTI ID:: 1843963

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 31 Vol. 125; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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