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

Masaaki Mitsui, Naoto Ando, Atsushi Nakajima

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24 Citations (Scopus)

Abstract

Photoelectron spectroscopy of tetracene cluster anions, (tetracene) n- (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 monomelic anion core is encompassed with geometrically reorganized neutral molecules. Conversely, a characteristic ion distribution in the mass spectrum of (tetracene)n- 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 ∼80% of that of the crystal, and the rest of the energy is provided by polarization of neutral molecules in adjacent layers.

Original languageEnglish
Pages (from-to)9644-9648
Number of pages5
JournalJournal of Physical Chemistry A
Volume111
Issue number39
DOIs
Publication statusPublished - 2007 Oct 4

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Photoelectron spectroscopy
Isomers
Anions
Mass spectrometry
mass spectroscopy
isomers
photoelectron spectroscopy
Polarization
analogs
anions
Crystals
polarization
detachment
spectroscopy
crystals
Molecules
energy
molecules
Structural relaxation
naphthacene

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "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",
abstract = "Photoelectron spectroscopy of tetracene cluster anions, (tetracene) n- (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 monomelic anion core is encompassed with geometrically reorganized neutral molecules. Conversely, a characteristic ion distribution in the mass spectrum of (tetracene)n- 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 ∼80{\%} of that of the crystal, and the rest of the energy is provided by polarization of neutral molecules in adjacent layers.",
author = "Masaaki Mitsui and Naoto Ando and Atsushi Nakajima",
year = "2007",
month = "10",
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language = "English",
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publisher = "American Chemical Society",
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T1 - Mass spectrometry and photoelectron spectroscopy of tetracene cluster anions, (tetracene)n- (n = 1-100)

T2 - Evidence for the highly localized nature of polarization in a cluster analogue of oligoacene crystals

AU - Mitsui, Masaaki

AU - Ando, Naoto

AU - Nakajima, Atsushi

PY - 2007/10/4

Y1 - 2007/10/4

N2 - Photoelectron spectroscopy of tetracene cluster anions, (tetracene) n- (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 monomelic anion core is encompassed with geometrically reorganized neutral molecules. Conversely, a characteristic ion distribution in the mass spectrum of (tetracene)n- 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 ∼80% of that of the crystal, and the rest of the energy is provided by polarization of neutral molecules in adjacent layers.

AB - Photoelectron spectroscopy of tetracene cluster anions, (tetracene) n- (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 monomelic anion core is encompassed with geometrically reorganized neutral molecules. Conversely, a characteristic ion distribution in the mass spectrum of (tetracene)n- 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 ∼80% of that of the crystal, and the rest of the energy is provided by polarization of neutral molecules in adjacent layers.

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