Dissociation of Polycyclic Aromatic Hydrocarbons: Molecular Dynamics Studies

Overview

Journal Philos Trans A Math Phys Eng Sci

Specialties Biomedical Engineering
Biophysics
Public Health

Date 2017 Mar 22

PMID 28320900

Citations 10

Authors

A Simon

M Rapacioli

G Rouaut

G Trinquier

F X Gadea

Affiliations

Soon will be listed here.

Abstract

We present dynamical studies of the dissociation of polycyclic aromatic hydrocarbon (PAH) radical cations in their ground electronic states with significant internal energy. Molecular dynamics simulations are performed, the electronic structure being described on-the-fly at the self-consistent-charge density functional-based tight binding (SCC-DFTB) level of theory. The SCC-DFTB approach is first benchmarked against DFT results. Extensive simulations are achieved for naphthalene [Formula: see text], pyrene [Formula: see text] and coronene [Formula: see text] at several energies. Such studies enable one to derive significant trends on branching ratios, kinetics, structures and hints on the formation mechanism of the ejected neutral fragments. In particular, dependence of branching ratios on PAH size and energy were retrieved. The losses of H and H (recognized as the ethyne molecule) were identified as major dissociation channels. The H/CH ratio was found to increase with PAH size and to decrease with energy. For [Formula: see text], which is the most interesting PAH from the astrophysical point of view, the loss of H was found as the quasi-only channel for an internal energy of 30 eV. Overall, in line with experimental trends, decreasing the internal energy or increasing the PAH size will favour the hydrogen loss channels with respect to carbonaceous fragments.This article is part of the themed issue 'Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces'.

Citing Articles

Addressing electronic and dynamical evolution of molecules and molecular clusters: DFTB simulations of energy relaxation in polycyclic aromatic hydrocarbons.

Rapacioli M, Buey M, Spiegelman F Phys Chem Chem Phys. 2023; 26(3):1499-1515.

PMID: 37933901 PMC: 10793726. DOI: 10.1039/d3cp02852f.

Low-Energy Transformation Pathways between Naphthalene Isomers.

Salomon G, Tarrat N, Schon J, Rapacioli M Molecules. 2023; 28(15).

PMID: 37570748 PMC: 10420886. DOI: 10.3390/molecules28155778.

Fingerprinting fragments of fragile interstellar molecules: dissociation chemistry of pyridine and benzonitrile revealed by infrared spectroscopy and theory.

Rap D, Simon A, Steenbakkers K, Schrauwen J, Redlich B, Brunken S Faraday Discuss. 2023; 245(0):221-244.

PMID: 37404008 PMC: 10510038. DOI: 10.1039/d3fd00015j.

The Accuracy of Semi-Empirical Quantum Chemistry Methods on Soot Formation Simulation.

Cong Y, Zhai Y, Chen X, Li H Int J Mol Sci. 2022; 23(21).

PMID: 36362159 PMC: 9657144. DOI: 10.3390/ijms232113371.

Formation of the acenaphthylene cation as a common CH-loss fragment in dissociative ionization of the PAH isomers anthracene and phenanthrene.

Banhatti S, Rap D, Simon A, Leboucher H, Wenzel G, Joblin C Phys Chem Chem Phys. 2022; 24(44):27343-27354.

PMID: 36326610 PMC: 9673687. DOI: 10.1039/d2cp03835h.

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