Kekulene: Structure, stability and nature of H•••H interactions in large PAHs

J. Poater; J. Paauwe; S. Pan; G. Merino; C. Fonseca Guerra; F. M. Bickelhaupt

doi:10.1016/j.molap.2017.05.003

Kekulene: Structure, stability and nature of H•••H interactions in large PAHs

J. Poater^*, J. Paauwe, S. Pan, G. Merino, C. Fonseca Guerra, F. M. Bickelhaupt

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

29 Downloads (Pure)

Abstract

We have quantum chemically analyzed how the stability of small and larger polycyclic aromatic hydrocarbons (PAHs) is determined by characteristic patterns in their structure using density functional theory at the BLYP/TZ2P level. In particular, we focus on the effect of the nonbonded H•••H interactions that occur in the bay region of kinked (or armchair) PAHs, but not in straight (or zigzag) PAHs. Model systems comprise anthracene, phenanthrene, and kekulene as well as derivatives thereof. Our main goals are: (1) to explore how nonbonded H•••H interactions in armchair configurations of kinked PAHs affect the geometry and stability of PAHs and how their effect changes as the number of such interactions in a PAH increases; (2) to understand the extent of stabilization upon the substitution of a bay C[sbnd]H fragment by either C^• or N; and (3) to examine the origin of such stabilizing/destabilizing interactions.

Original language	English
Pages (from-to)	19-26
Number of pages	8
Journal	Molecular Astrophysics
Volume	8
Early online date	26 May 2017
DOIs	https://doi.org/10.1016/j.molap.2017.05.003
Publication status	Published - 1 Sept 2017

Funding

We thank the Netherlands Organization for Scientific Research (NWO) for financial support through the Dutch Astrochemistry Network (DAN) and the Spanish MINECO (project CTQ2016-77558-R). The work in Mexico was funded by Conacyt (Grant CB-2015-252356).

Funders	Funder number
Dutch Astrochemistry Network
Consejo Nacional de Ciencia y Tecnología	CB-2015-252356
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Ministerio de Economía y Competitividad	CTQ2016-77558-R

Keywords

DFT calculations
Energy decomposition analysis (EDA)
H stripping
H•••H interaction
Kekulene
N[sbnd]heterocycles
Polycyclic aromatic hydrocarbons (PAHs)

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1016/j.molap.2017.05.003

Kekulene Structure, stability and nature of H•••H interactions in large PAHsFinal published version, 1.24 MBLicence: Article 25fa Dutch Copyright Act

Persistent URL (handle)

Persistent link

Cite this

@article{2414bce884d14761b9ea3e6e8fe7ac31,

title = "Kekulene: Structure, stability and nature of H•••H interactions in large PAHs",

abstract = "We have quantum chemically analyzed how the stability of small and larger polycyclic aromatic hydrocarbons (PAHs) is determined by characteristic patterns in their structure using density functional theory at the BLYP/TZ2P level. In particular, we focus on the effect of the nonbonded H•••H interactions that occur in the bay region of kinked (or armchair) PAHs, but not in straight (or zigzag) PAHs. Model systems comprise anthracene, phenanthrene, and kekulene as well as derivatives thereof. Our main goals are: (1) to explore how nonbonded H•••H interactions in armchair configurations of kinked PAHs affect the geometry and stability of PAHs and how their effect changes as the number of such interactions in a PAH increases; (2) to understand the extent of stabilization upon the substitution of a bay C[sbnd]H fragment by either C• or N; and (3) to examine the origin of such stabilizing/destabilizing interactions.",

keywords = "DFT calculations, Energy decomposition analysis (EDA), H stripping, H•••H interaction, Kekulene, N[sbnd]heterocycles, Polycyclic aromatic hydrocarbons (PAHs)",

author = "J. Poater and J. Paauwe and S. Pan and G. Merino and Guerra, {C. Fonseca} and Bickelhaupt, {F. M.}",

year = "2017",

month = sep,

day = "1",

doi = "10.1016/j.molap.2017.05.003",

language = "English",

volume = "8",

pages = "19--26",

journal = "Molecular Astrophysics",

issn = "2405-6758",

publisher = "Elsevier B.V.",

}

TY - JOUR

T1 - Kekulene: Structure, stability and nature of H•••H interactions in large PAHs

AU - Poater, J.

AU - Paauwe, J.

AU - Pan, S.

AU - Merino, G.

AU - Guerra, C. Fonseca

AU - Bickelhaupt, F. M.

PY - 2017/9/1

Y1 - 2017/9/1

N2 - We have quantum chemically analyzed how the stability of small and larger polycyclic aromatic hydrocarbons (PAHs) is determined by characteristic patterns in their structure using density functional theory at the BLYP/TZ2P level. In particular, we focus on the effect of the nonbonded H•••H interactions that occur in the bay region of kinked (or armchair) PAHs, but not in straight (or zigzag) PAHs. Model systems comprise anthracene, phenanthrene, and kekulene as well as derivatives thereof. Our main goals are: (1) to explore how nonbonded H•••H interactions in armchair configurations of kinked PAHs affect the geometry and stability of PAHs and how their effect changes as the number of such interactions in a PAH increases; (2) to understand the extent of stabilization upon the substitution of a bay C[sbnd]H fragment by either C• or N; and (3) to examine the origin of such stabilizing/destabilizing interactions.

AB - We have quantum chemically analyzed how the stability of small and larger polycyclic aromatic hydrocarbons (PAHs) is determined by characteristic patterns in their structure using density functional theory at the BLYP/TZ2P level. In particular, we focus on the effect of the nonbonded H•••H interactions that occur in the bay region of kinked (or armchair) PAHs, but not in straight (or zigzag) PAHs. Model systems comprise anthracene, phenanthrene, and kekulene as well as derivatives thereof. Our main goals are: (1) to explore how nonbonded H•••H interactions in armchair configurations of kinked PAHs affect the geometry and stability of PAHs and how their effect changes as the number of such interactions in a PAH increases; (2) to understand the extent of stabilization upon the substitution of a bay C[sbnd]H fragment by either C• or N; and (3) to examine the origin of such stabilizing/destabilizing interactions.

KW - DFT calculations

KW - Energy decomposition analysis (EDA)

KW - H stripping

KW - H•••H interaction

KW - Kekulene

KW - N[sbnd]heterocycles

KW - Polycyclic aromatic hydrocarbons (PAHs)

UR - http://www.scopus.com/inward/record.url?scp=85020245317&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85020245317&partnerID=8YFLogxK

U2 - 10.1016/j.molap.2017.05.003

DO - 10.1016/j.molap.2017.05.003

M3 - Article

AN - SCOPUS:85020245317

SN - 2405-6758

VL - 8

SP - 19

EP - 26

JO - Molecular Astrophysics

JF - Molecular Astrophysics

ER -

Kekulene: Structure, stability and nature of H•••H interactions in large PAHs

Abstract

Funding

Keywords

UN SDGs

Access to Document

Persistent URL (handle)

Other files and links

Fingerprint

Cite this