Doping Capabilities of Fluorine on the UV Absorption and Emission Spectra of Pyrene-Based Graphene Quantum Dots

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F20%3A00537751" target="_blank" >RIV/61388963:_____/20:00537751 - isvavai.cz</a>

Result on the web

<a href="https://doi.org/10.1021/acs.jpca.0c08694" target="_blank" >https://doi.org/10.1021/acs.jpca.0c08694</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpca.0c08694" target="_blank" >10.1021/acs.jpca.0c08694</a>

Result language

angličtina

Original language name

Doping Capabilities of Fluorine on the UV Absorption and Emission Spectra of Pyrene-Based Graphene Quantum Dots

Original language description

Functionalization of quantum carbon dots (QCDs) and graphene quantum dots (GQDs) is a popular way to tune their optical spectra increasing their potential applicability in material science and biorelated disciplines. Based on the experimental observation, functionalization by fluorine atoms induces substantial shifts in absorption and emission spectra and an intensity increase. Understanding of the effects due to fluorine functionalization at the atomic scale level is still challenging due to the complex structure of fluorinated QCDs. In this work, the effect of covalent edge-fluorination and fluorine anion doping on absorption and emission spectra of prototypical polycyclic aromatic hydrocarbons pyrene and circum-pyrene has been investigated. The ways to achieve efficient red-shifts in the UV spectra and obtaining reasonable intensities stood in the focus of the work. High-level quantum chemical methods based on density functional theory/multireference configuration interaction (DFT/MRCI) and single-reference second-order algebraic diagrammatic construction (ADC(2)) and density functional theory (DFT) using the CAM-B3LYP functional have been used for this purpose. The calculations show that doping with the fluoride anion can have significant effects on the electronic spectrum. However, the effect of the fluoride ion is strongly dependent on its position with respect to the QCD. The localization above the GQDs causes large red-shifts to both the absorption and emission of spectra of GQDs, while in-plane localization leads to only negligible shifts and a tendency to dissociation after electronic excitation. Thus, large red-shifts, observed in complexes with F-, are obtained due to the introduction of new excited states with large CT character not yet been considered previously in this context, although they have the potential to significantly influence the photophysics of quantum dots. Doping by edge fluorination redshifts the spectra only slightly. This study provides insights on fluorine-doped GQDs, which is conducive to promoting its rational design and controllable synthesis.

Czech name

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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

<a href="/en/project/GA18-09914S" target="_blank" >GA18-09914S: Formation of covalent molecular complexes on surfaces driven by light induced chemical reactions</a><br>

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

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

—

Volume of the periodical

124

Issue of the periodical within the volume

52

Country of publishing house

US - UNITED STATES

Number of pages

13

Pages from-to

10954-10966

UT code for WoS article

000608856500004

EID of the result in the Scopus database

2-s2.0-85098759859