Charge-Transfer Processes in Surface-Enhanced Raman Scattering. Franck−Condon Active Vibrations of Pyrazine
SERS spectra of pyrazine on silver electrode have been recorded and analyzed, assuming a charge transfer effect and using selection rules analogous to those of resonance Raman. With the aim of predicting the effect of this mechanism on the selective enhancement of fundamentals, a method has been pro...
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| Published in: | Journal of physical chemistry (1952) Vol. 100; no. 8; pp. 3199 - 3206 |
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| Format: | Journal Article |
| Language: | English |
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American Chemical Society
22-02-1996
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| Abstract | SERS spectra of pyrazine on silver electrode have been recorded and analyzed, assuming a charge transfer effect and using selection rules analogous to those of resonance Raman. With the aim of predicting the effect of this mechanism on the selective enhancement of fundamentals, a method has been proposed based on an analysis of the results of geometry optimizations carried out by ab initio calculations. The strongest SERS bands coincide with those assigned to the normal modes connecting the equilibrium geometries of the neutral molecule and the radical anion. These results support the presence of a charge transfer process from the metal to the adsorbate in the SERS spectra of pyrazine where a significant enhancement of vibrations 8a, 9a, 1, and 6a can be observed. The prediction capability of the analysis proposed here has been checked with published resonance Raman spectra of pyrazine and pyrazine-d 4. In all of the cases the strongest bands in the spectra are directly related to the largest ΔQ values obtained through the transformation ΔQ = L -1ΔR. |
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| AbstractList | SERS spectra of pyrazine on silver electrode have been recorded and analyzed, assuming a charge transfer effect and using selection rules analogous to those of resonance Raman. With the aim of predicting the effect of this mechanism on the selective enhancement of fundamentals, a method has been proposed based on an analysis of the results of geometry optimizations carried out by ab initio calculations. The strongest SERS bands coincide with those assigned to the normal modes connecting the equilibrium geometries of the neutral molecule and the radical anion. These results support the presence of a charge transfer process from the metal to the adsorbate in the SERS spectra of pyrazine where a significant enhancement of vibrations 8a, 9a, 1, and 6a can be observed. The prediction capability of the analysis proposed here has been checked with published resonance Raman spectra of pyrazine and pyrazine-d 4. In all of the cases the strongest bands in the spectra are directly related to the largest ΔQ values obtained through the transformation ΔQ = L -1ΔR. |
| Author | Arenas, Juan Francisco Woolley, Mark Steven Otero, Juan Carlos Marcos, Juan Ignacio |
| Author_xml | – sequence: 1 givenname: Juan Francisco surname: Arenas fullname: Arenas, Juan Francisco – sequence: 2 givenname: Mark Steven surname: Woolley fullname: Woolley, Mark Steven – sequence: 3 givenname: Juan Carlos surname: Otero fullname: Otero, Juan Carlos – sequence: 4 givenname: Juan Ignacio surname: Marcos fullname: Marcos, Juan Ignacio |
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| Cites_doi | 10.1021/j150642a007 10.1063/1.441580 10.1063/1.441914 10.1103/RevModPhys.57.783 10.1021/j100123a004 10.1002/bbpc.19840880409 10.1016/0009-2614(80)85112-8 10.1021/la00079a012 10.1002/anie.198601311 10.1063/1.446266 10.1016/0009-2614(74)85388-1 10.1021/j100315a019 10.1016/0039-6028(86)90216-5 10.1103/PhysRevLett.35.1429 10.1063/1.430700 10.1021/cr00005a012 10.1016/0584-8539(86)80242-2 10.1016/0022-2860(90)87007-K 10.1016/0009-2614(79)80525-4 10.1063/1.466618 10.1039/f29858100405 10.1016/0022-2852(64)90113-4 10.1021/ed054p474 10.1021/j100029a015 10.1021/ja00504a009 10.1021/j100393a013 10.1016/0368-2048(87)80059-2 10.1021/j100140a015 10.1016/0009-2614(82)83595-1 10.1063/1.454704 10.1021/j100099a038 10.1146/annurev.pc.39.100188.002143 10.1021/ja00483a010 10.1088/0953-8984/4/5/001 10.1016/S0022-0728(77)80224-6 10.1063/1.465346 10.1063/1.440142 10.1063/1.459619 |
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| Copyright | Copyright © 1996 American Chemical Society |
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| Snippet | SERS spectra of pyrazine on silver electrode have been recorded and analyzed, assuming a charge transfer effect and using selection rules analogous to those of... |
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| Title | Charge-Transfer Processes in Surface-Enhanced Raman Scattering. Franck−Condon Active Vibrations of Pyrazine |
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