Hole-vibration coupling of the highest occupied state in pentacene thin films

The hole-vibration coupling of the highest occupied state in pentacene thin films on graphite is studied by high-resolution ultraviolet photoelectron spectroscopy. Vibration satellites in the film show a take-off-angle dependence, indicating that the Franck-Condon principle is not strictly satisfied in this system. They are more intense than in the gas phase and the vibrational energy in the film is slightly lower than that in the gas phase. This demonstrates that the reorganization energy in pentacene thin films is slightly larger than that estimated from the photoelectron spectrum of free pentacene molecules. Furthermore, it is pointed out that the electron hopping in the low-temperature film may occur in the femtosecond scale before the electronic polarization of the surrounding medium is completed. © 2005 The American Physical Society.

[1]  Hirohiko Fukagawa,et al.  Photoelectron fine structures of uppermost valence band for well-characterized ClAl-phthalocyanine ultrathin film: UPS and MAES study , 2004 .

[2]  K. Seki,et al.  Intermolecular energy-band dispersion in PTCDA multilayers , 2003 .

[3]  E. A. Silinsh,et al.  Molecular polaron states in polyacene crystals. Formation and transfer processes , 1995 .

[4]  N. Ueno,et al.  Very narrow photoemission bandwidth of the highest occupied state in a copper-phthalocyanine monolayer , 2002 .

[5]  M. Lannoo,et al.  Electron-phonon coupling for aromatic molecular crystals: Possible consequences for their superconductivity , 1998 .

[6]  J. Brédas,et al.  Hole- and electron-vibrational couplings in oligoacene crystals: intramolecular contributions. , 2002, Physical review letters.

[7]  H. Hövel,et al.  Cluster-Substrate Interaction on a Femtosecond Time Scale Revealed by a High-Resolution Photoemission Study of the Fermi-Level Onset , 1998 .

[8]  P. A. Brühwiler,et al.  Vibronic coupling in the photoemission bands of condensed C60 , 1997 .

[9]  H. Ozaki Growth of organic ultrathin films studied by Penning ionization electron and ultraviolet photoelectron spectroscopies: Pentacene , 2000 .

[10]  Umbach,et al.  Photoemission line shapes of adsorbates: Conclusions from the analysis of vibration-resolved N2 spectra. , 1990, Physical review letters.

[11]  Palmer,et al.  Orientation-dependent final-state effects in photoelectron spectra of physisorbed molecules. , 1992, Physical review letters.

[12]  Kessler,et al.  Photoemission spectra of C60-: Electron-phonon coupling, Jahn-Teller effect, and superconductivity in the fullerides. , 1995, Physical review letters.

[13]  T. Yamabe,et al.  Vibronic interactions and superconductivity in acene anions and cations , 2001 .

[14]  W. R. Salaneck Intermolecular Relaxation Energies in Anthracene , 1978 .

[15]  K. Seki,et al.  High-resolution Photoelectron Spectroscopy of Naphthacene Polycrystal by Means of Helium 21.22 eV Resonance Line , 1974 .

[16]  E. A. Silinsh,et al.  Dynamics of electronic polarization in molecular crystals , 1995 .

[17]  W. Eberhardt,et al.  Vibrational Bands in the Photoemission of an Adsorbate:O2on Graphite , 1981 .

[18]  Hansen,et al.  Hopping of the photohole during photoemission from physisorbed N2: The influence of band formation on vibrational excitation. , 1991, Physical review letters.

[19]  David Beljonne,et al.  Charge-transfer and energy-transfer processes in pi-conjugated oligomers and polymers: a molecular picture. , 2004, Chemical reviews.

[20]  W. R. Salaneck,et al.  Vibronic coupling in the ground and excited states of the naphthalene cation. , 2004, Chemical communications.

[21]  Yoyo Hinuma,et al.  HOMO-band fine structure of OTi- and Pb-phthalocyanine ultrathin films: effects of the electric dipole layer , 2004 .