Tuning the UV spectrum of PAHs by means of different N-doping types taking pyrene as paradigmatic example: categorizationviavalence bond theory and high-level computational approaches

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F20%3A00533461" target="_blank" >RIV/61388963:_____/20:00533461 - isvavai.cz</a>

Alternative codes found

RIV/61989592:15310/20:73604176

Result on the web

<a href="https://doi.org/10.1039/D0CP02688C" target="_blank" >https://doi.org/10.1039/D0CP02688C</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d0cp02688c" target="_blank" >10.1039/d0cp02688c</a>

Result language

angličtina

Original language name

Tuning the UV spectrum of PAHs by means of different N-doping types taking pyrene as paradigmatic example: categorizationviavalence bond theory and high-level computational approaches

Original language description

Tuning of the electronic spectra of carbon dots by means of inserting heteroatoms into the pi-conjugated polycyclic aromatic hydrocarbon (PAH) system is a popular tool to achieve a broad range of absorption and emission frequencies. Especially nitrogen atoms have been used successfully for that purpose. Despite the significant progress achieved with these procedures, the prediction of specific shifts in the UV-vis spectra and the understanding of the electronic transitions is still a challenging task. In this work, high-level quantum chemical methods based on multireference (MR) and single-reference (SR) methods have been used to predict the effect of different nitrogen doping patterns inserted into the prototypical PAH pyrene on its absorption spectrum. Furthermore, a simple classification scheme based on valence bond (VB) theory and the Clar sextet rule in combination with the harmonic oscillator measure of aromaticity (HOMA) index was applied to arrange the different doping structures into groups and rationalize their electronic properties. The results show a wide variety of mostly redshifts in the spectra as compared to the pristine pyrene case. The most interesting doping structures with the largest red shifts leading to absorption energies below one eV could be readily explained by the occurrence of diradical VB structures in combination with Clar sextets. Moreover, analysis of the electronic transitions computed with MR methods showed that several of the low-lying excited states possess double-excitation character, which cannot be realized by the popular SR methods and, thus, are simply absent in the calculated spectra.

Czech name

—

Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

Result was created during the realization of more than one project. More information in the Projects tab.

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2020

Confidentiality

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

Name of the periodical

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

—

Volume of the periodical

22

Issue of the periodical within the volume

38

Country of publishing house

GB - UNITED KINGDOM

Number of pages

13

Pages from-to

22003-22015

UT code for WoS article

000576194400039

EID of the result in the Scopus database

2-s2.0-85092681336