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Photon-driven charge transfer and Herzberg-Teller vibronic coupling mechanism in surface-enhanced Raman scattering of p-aminothiophenol adsorbed on coinage metal surfaces: A density functional theory study
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10.1063/1.3643766
/content/aip/journal/jcp/135/13/10.1063/1.3643766
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/13/10.1063/1.3643766

Figures

Image of FIG. 1.
FIG. 1.

Schematic models of PATP interacting with metal clusters in single-end configurations via the sulfur atom, (a) Au13-PATP, (b) Ag13-PATP, and (c) Cu13-PATP and in double-end configurations via both thiol and amino group, (d) Au13-PATP-Au4, (e) Ag13-PATP-Ag4, (f) Cu13-PATP-Cu4, (g) Au13-PATP-Ag4, (h) Au13-PATP-Cu4, (i) Ag13-PATP-Au4, (j) Ag13-PATP-Cu4, (k) Cu13-PATP-Au4, and (l) Cu13-PATP-Ag4.

Image of FIG. 2.
FIG. 2.

Frontier molecular orbitals of aniline (a) and PATP (b). The symmetric representations are assumed under an approximate C2v symmetric point group. The axes were chosen as that the molecule plane is in the yz plane and z is along the C2 axis here. The orbital levels are referred to the vacuum level.

Image of FIG. 3.
FIG. 3.

Calculated UV absorption spectrum of the free PATP molecule by TD-DFT with B3LYP/6-311+G(d, p). The absorption line shape was calculated as a sum of Lorentzian bands with a half-bandwidth γ = 1000 cm−1.

Image of FIG. 4.
FIG. 4.

Calculated pre-resonance Raman spectra of PATP with different Raman excitation lines. The incident wavelengths are chosen to have energy gaps of 0.1 and 0.2 eV higher and lower with respect to the S1 excited state. The b2 modes in the wavenumber region of 1000 to 1650 cm−1 are marked with short dashed lines.

Image of FIG. 5.
FIG. 5.

Schematic diagrams of the photon-driven charge transfer from PATP to metals. (Left) The excitation energy matches the energy gap between the HOMO orbital of adsorbed PATP and Fermi level of metals in the CT process. (Right) The relevant energy states involved in the electronic and vibrational levels in the CT process.

Image of FIG. 6.
FIG. 6.

Calculated off-resonance and pre-resonance Raman spectra of (a) Au13-PATP and (b) Ag13-PATP at B3LYP/6-311+G(d, p)/LAN2DZ level. The first two incident wavelengths were chosen to have energy gaps of 0.1 and 0.2 eV with respect to the low-lying CT excited state.

Image of FIG. 7.
FIG. 7.

Simulated non-resonance Raman spectra of (a) Au13-PATP-Au4, (b) Ag13-PATP-Ag4, and (c) Cu13-PATP-Cu4 at B3LYP/6-311+G(d, p)/LAN2DZ level. An excitation wavelength of 632.8 nm and a linewidth of 10 cm−1 are used in the simulated spectra.

Image of FIG. 8.
FIG. 8.

Simulated non-resonance Raman spectra of PATP trapped into heterojunctions. The NH2 wagging mode and C–N stretching mode are labeled with a red asterisk and a blue dot, respectively.

Image of FIG. 9.
FIG. 9.

Simulated pre-resonance Raman spectra of (1) Au13-PATP-Au4, (2) Ag13-PATP-Ag4, (3) Au13-PATP-Ag4, and (4) Ag13-PATP-Au4 with the incident wavelength of 1064 nm.

Tables

Generic image for table
Table I.

Vibrational vectors, frequencies (ω, cm−1), and Raman activities (I, Å4/amu) of all the b2 modes in the range of 1000 to 1650 cm−1. The relative Raman intensities defined as a ratio with respect to the a1-type mode at 1088 cm−1 are given in parenthesis.

Generic image for table
Table II.

Calculated vertical transition energies (ΔE) and oscillator strength (f) of the low-lying molecule-to-metal and metal-to-molecule CT transitions and correspond molecular orbitals involved in Au13-PATP, Ag13-PATP, and Cu13-PATP by TD-B3LYP/6-311+G(d, p)/LAN2DZ.

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/content/aip/journal/jcp/135/13/10.1063/1.3643766
2011-10-06
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Photon-driven charge transfer and Herzberg-Teller vibronic coupling mechanism in surface-enhanced Raman scattering of p-aminothiophenol adsorbed on coinage metal surfaces: A density functional theory study
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/13/10.1063/1.3643766
10.1063/1.3643766
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