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

Liu, Jin; Adamska, Lyudmyla; Doorn, Stephen K.; Tretiak, Sergei

doi:10.1039/c5cp01782c

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

Journal Article · Thu May 14 00:00:00 EDT 2015 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c5cp01782c· OSTI ID:1221617

Liu, Jin ^[1]; Adamska, Lyudmyla ^[2]; Doorn, Stephen K. ^[2]; Tretiak, Sergei ^[2]

Univ. of Rochester, Rochester, NY (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

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.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC52-06NA25396

OSTI ID:: 1221617

Report Number(s):: LA-UR-15-24438; PPCPFQ

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 17, Issue 22; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 19 works

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