610 research outputs found
Do coupling exciton and oscillation of electron-hole pair exist in neutral and charged pi-dimeric quinquethiophenes?
Optical physical properties of neutral and charged quinquethiophene monomer, and neutral and cationic pi-dimeric quinquethiophenes were investigated with density functional theory as well as the two dimensional (2D) site (transition density matrix) and three dimensional (3D) cube (transition density and charge difference density) representations, stimulated by the recent experimental report [T. Sakai , J. Am. Chem. Soc. 127, 8082 (2005)]. Transition density shows the orientation and strength of the transition dipole moment of neutral and charged quinquethiophene monomer, and charge difference density reveals the orientation and result of the charge transfer in neutral and charged quinquethiophene monomer. To study if coupling exciton and oscillation of electron-hole pair exist in neutral and cationic pi-dimeric quinquethiophenes, the coupling constants J (coupling exciton of electron-hole pair) and K (coupling oscillation of electron-hole pair) were introduced to the exciton coordinate and momentum operators, respectively, and the 2D and 3D analysis methods were further developed by extending our previous theoretical methods [M. T. Sun, J. Chem. Phys. 124, 054903 (2006)]. With the new developed 2D and 3D analysis methods, we investigated the excited state properties of neutral and cationic pi-dimeric quinquethiophenes, especially on the coupling exciton and oscillation of electron-hole pair between monomers. The 2D results show that there is neither coupling exciton (J=0) nor oscillation (K=0) of electron-hole pair in neutral pi-dimeric quinquethiophenes. For some excited states of cationic pi-dimeric quinquethiophenes, there is no coupling exciton (J=0), but there is coupling oscillation (K not equal 0); while for some excited states, there are both coupling exciton and coupling oscillator simultaneously (J not equal 0 and K not equal 0). The strength of transition dipole moments of pi-dimeric quinquethiophenes were interpreted with 3D transition density, which reveals the orientations of their two subtransition dipole moments. The 3D charge transition density reveals the orientation and result of intermonomer and/or intramonomer charge transfer. The calculated results reveal that excited state properties of neutral pi-dimeric quinquethiophene are significantly different from those of the cationic pi-dimeric quinquethiophenes
Photoemission electron microscopy of localized surface plasmons in silver nanostructures at telecommunication wavelengths
We image the field enhancement at Ag nanostructures using femtosecond laser
pulses with a center wavelength of 1.55 micrometer. Imaging is based on
non-linear photoemission observed in a photoemission electron microscope
(PEEM). The images are directly compared to ultra violet PEEM and scanning
electron microscopy (SEM) imaging of the same structures. Further, we have
carried out atomic scale scanning tunneling microscopy (STM) on the same type
of Ag nanostructures and on the Au substrate. Measuring the photoelectron
spectrum from individual Ag particles shows a larger contribution from higher
order photoemission process above the work function threshold than would be
predicted by a fully perturbative model, consistent with recent results using
shorter wavelengths. Investigating a wide selection of both Ag nanoparticles
and nanowires, field enhancement is observed from 30% of the Ag nanoparticles
and from none of the nanowires. No laser-induced damage is observed of the
nanostructures neither during the PEEM experiments nor in subsequent SEM
analysis. By direct comparison of SEM and PEEM images of the same
nanostructures, we can conclude that the field enhancement is independent of
the average nanostructure size and shape. Instead, we propose that the
variations in observed field enhancement could originate from the wedge
interface between the substrate and particles electrically connected to the
substrate
Activated Vibrational Modes and Fermi Resonance in Tip-Enhanced Raman Spectroscopy
Using p-aminothiophenol (PATP) molecules on a gold substrate as prototypical
examples and high vacuum tip-enhanced Raman spectroscopy (HV-TERS), we show
that the vibrational spectra of those molecules are distinctly different from
those in typical surface-enhanced Raman spectroscopy. Detailed first-principles
calculations help to assign the Raman peaks in the TERS measurements as Raman
active and infrared (IR) active vibrational modes of dimercaptoazobenzene
(DMAB), thus providing strong spectroscopic evidence for the conversion of PATP
dimerization to DMAB. The activation of the IR active modes is due to enhanced
electromagnetic field gradient effects within the gap region of the highly
asymmetric tip-surface geometry. Our TERS measurements also realize splitting
of certain vibrational modes due to Fermi resonance between a fundamental mode
and the overtone of a different mode or a combinational mode. These findings
help to broaden the versatility of TERS as a promising technique for
ultrasensitive molecular spectroscopy
- …