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Title: Singlet and triplet excitons and charge polarons in cycloparaphenylenes. A density functional theory study

Abstract

Conformational structure and the electronic properties of various electronic excitations in cycloparaphenylenes (CPPs) are calculated using hybrid Density Functional Theory (DFT). The results demonstrate that wavefunctions of singlet and triplet excitons as well as the positive and negative polarons remain fully delocalized in CPPs. In contrast, these excitations in larger CPP molecules become localized on several phenyl rings, which are locally planarized, while the undeformed ground state geometry is preserved on the rest of the hoop. As evidenced by the measurements of bond-length alternation and dihedral angles, localized regions show stronger hybridization between neighboring bonds and thus enhanced electronic communication. This effect is even more significant in the smaller hoops, where phenyl rings have strong quinoid character in the ground state. Thus, upon excitation, electron–phonon coupling leads to the self-trapping of the electronic wavefunction and release of energy from fractions of an eV up to two eVs, depending on the type of excitation and the size of the hoop. The impact of such localization on electronic and optical properties of CPPs is systematically investigated and compared with the available experimental measurements.

Authors:
 [1];  [2];  [2];  [2]
+ Show Author Affiliations
  1. Univ. of Rochester, Rochester, NY (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1221617
Report Number(s):
LA-UR-15-24438
Journal ID: ISSN 1463-9076; PPCPFQ
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 17; Journal Issue: 22; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Liu, Jin, Adamska, Lyudmyla, Doorn, Stephen K., and Tretiak, Sergei. Singlet and triplet excitons and charge polarons in cycloparaphenylenes. A density functional theory study. United States: N. p., 2015. Web. doi:10.1039/c5cp01782c.
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Liu, Jin, Adamska, Lyudmyla, Doorn, Stephen K., & Tretiak, Sergei. Singlet and triplet excitons and charge polarons in cycloparaphenylenes. A density functional theory study. United States. https://doi.org/10.1039/c5cp01782c
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Liu, Jin, Adamska, Lyudmyla, Doorn, Stephen K., and Tretiak, Sergei. Thu . "Singlet and triplet excitons and charge polarons in cycloparaphenylenes. A density functional theory study". United States. https://doi.org/10.1039/c5cp01782c. https://www.osti.gov/servlets/purl/1221617.
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@article{osti_1221617,
title = {Singlet and triplet excitons and charge polarons in cycloparaphenylenes. A density functional theory study},
author = {Liu, Jin and Adamska, Lyudmyla and Doorn, Stephen K. and Tretiak, Sergei},
abstractNote = {Conformational structure and the electronic properties of various electronic excitations in cycloparaphenylenes (CPPs) are calculated using hybrid Density Functional Theory (DFT). The results demonstrate that wavefunctions of singlet and triplet excitons as well as the positive and negative polarons remain fully delocalized in CPPs. In contrast, these excitations in larger CPP molecules become localized on several phenyl rings, which are locally planarized, while the undeformed ground state geometry is preserved on the rest of the hoop. As evidenced by the measurements of bond-length alternation and dihedral angles, localized regions show stronger hybridization between neighboring bonds and thus enhanced electronic communication. This effect is even more significant in the smaller hoops, where phenyl rings have strong quinoid character in the ground state. Thus, upon excitation, electron–phonon coupling leads to the self-trapping of the electronic wavefunction and release of energy from fractions of an eV up to two eVs, depending on the type of excitation and the size of the hoop. The impact of such localization on electronic and optical properties of CPPs is systematically investigated and compared with the available experimental measurements.},
doi = {10.1039/c5cp01782c},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 22,
volume = 17,
place = {United States},
year = {Thu May 14 00:00:00 EDT 2015},
month = {Thu May 14 00:00:00 EDT 2015}
}
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https://doi.org/10.1039/c5cp01782c
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