The optical behavior of poly(para-phenylene vinylene) is explored through an ab initio scheme based on the Bethe-Salpeter equation, where the electron-hole interaction is included on top of a density functional theory calculation. Results for different solid-state packings are reviewed, demonstrating that the details of crystalline arrangement dramatically alter the optical properties and lead to a rich excitonic structure, where also charge-transfer states appear (electron and hole on different chains). Moreover, for a typical herringbone packing the excitonic state of the isolated molecule splits in two direct components (with electron and hole on the same chain), one for each non-translationally-invariant chain in the unit cell, and the optical inactivity of the lowest component can crucially quench the luminescence efficiency. Besides the far-field absorption spectra and the description of the excitonic states, a formalism to simulate the near-field spectra is presented that allows one to detect also excitonic states that are dipole-forbidden in the far-field spectra.

Ab initio optical absorption in conjugated polymers: the role of dimensionality, / Ruini, Alice. - ELETTRONICO. - T109:(2004), pp. 121-127. (Intervento presentato al convegno EXCITiNG Summer School: DFT Beyond the Ground State tenutosi a Riksgransen, swe nel 2003) [10.1238/Physica.Topical.109a00121].

Ab initio optical absorption in conjugated polymers: the role of dimensionality,

RUINI, Alice
2004

Abstract

The optical behavior of poly(para-phenylene vinylene) is explored through an ab initio scheme based on the Bethe-Salpeter equation, where the electron-hole interaction is included on top of a density functional theory calculation. Results for different solid-state packings are reviewed, demonstrating that the details of crystalline arrangement dramatically alter the optical properties and lead to a rich excitonic structure, where also charge-transfer states appear (electron and hole on different chains). Moreover, for a typical herringbone packing the excitonic state of the isolated molecule splits in two direct components (with electron and hole on the same chain), one for each non-translationally-invariant chain in the unit cell, and the optical inactivity of the lowest component can crucially quench the luminescence efficiency. Besides the far-field absorption spectra and the description of the excitonic states, a formalism to simulate the near-field spectra is presented that allows one to detect also excitonic states that are dipole-forbidden in the far-field spectra.
2004
EXCITiNG Summer School: DFT Beyond the Ground State
Riksgransen, swe
2003
T109
121
127
Ruini, Alice
Ab initio optical absorption in conjugated polymers: the role of dimensionality, / Ruini, Alice. - ELETTRONICO. - T109:(2004), pp. 121-127. (Intervento presentato al convegno EXCITiNG Summer School: DFT Beyond the Ground State tenutosi a Riksgransen, swe nel 2003) [10.1238/Physica.Topical.109a00121].
File in questo prodotto:
Non ci sono file associati a questo prodotto.
Pubblicazioni consigliate

Licenza Creative Commons
I metadati presenti in IRIS UNIMORE sono rilasciati con licenza Creative Commons CC0 1.0 Universal, mentre i file delle pubblicazioni sono rilasciati con licenza Attribuzione 4.0 Internazionale (CC BY 4.0), salvo diversa indicazione.
In caso di violazione di copyright, contattare Supporto Iris

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/457944
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 1
  • ???jsp.display-item.citation.isi??? 1
social impact