Papers

Peer-reviewed
Oct, 2007

Mass spectrometry and photoelectron spectroscopy of tetracene cluster anions, (Tetracene)(n)(-) (n=1-100): Evidence for the highly localized nature of polarization in a cluster analogue of oligoacene crystals

JOURNAL OF PHYSICAL CHEMISTRY A
  • Masaaki Mitsui
  • ,
  • Naoto Ando
  • ,
  • Atsushi Nakajima

Volume
111
Number
39
First page
9644
Last page
9648
Language
English
Publishing type
Research paper (scientific journal)
DOI
10.1021/jp076134h
Publisher
AMER CHEMICAL SOC

Photoelectron spectroscopy of tetracene cluster anions, (tetracene), (n = 1 - 100), reveals the coexistence of two types of isomers, designated as isomers I and II-1 (n = 10-50) or isomers I and II-2 (n > 60), in a wide size range. The vertical detachment energies (VDEs) of isomer I increase persistently due to polarization and structural relaxation effects, where a monomeric anion core is encompassed with geometrically reorganized neutral molecules. Conversely, a characteristic ion distribution in the mass spectrum of (tetracene),, ensues from the two-dimensional (2D) herringbone-type ordering of isomer II-1, whose VDEs remain constant at 1.80 eV for n >= 14. Also, isomer II-2, presumably adopting multilayered structural motifs, exhibits invariable VDEs of 2.0 eV, a manifestation of significant charge screening effects in these isomers. The invariable nature of the VDEs of isomers II-1 and II-2 unambiguously demonstrates a largely localized nature of polarization induced by the excess charge residing in microscopic crystal-like environments. Surprisingly, only 14 tetracene molecules within a 2D herringbone-type layer including an excess charge can provide the charge stabilization energy corresponding to similar to 80% of that of the crystal, and the rest of the energy is provided by polarization of neutral molecules in adjacent layers.

Link information
DOI
https://doi.org/10.1021/jp076134h
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000249838100002&DestApp=WOS_CPL
ID information
  • DOI : 10.1021/jp076134h
  • ISSN : 1089-5639
  • Web of Science ID : WOS:000249838100002

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