Understanding the molecule-surface chemical coupling in SERS

Seth M. Morton, Lasse Jensen

Research output: Contribution to journalArticle

237 Citations (Scopus)

Abstract

The enhancement mechanism due to the molecule-surface chemical coupling in surface-enhanced Raman scattering (SERS) has been characterized using time-dependent density functional theory. This has been achieved with a systematical study of the chemical enhancement of meta-and para-substituted pyridines interacting with a small silver cluster (Ag 20). Changing the functional groups on pyridine enabled us to modulate the direct chemical interactions between the pyridine ring and the metal cluster. Surprisingly, we find that the enhancement does not increase as more charge is transferred from the pyridine ring to the cluster. Instead, we find that the magnitude of chemical enhancement is governed to a large extent by the energy difference between the highest occupied energy level (HOMO) of the metal and the lowest unoccupied energy level (LUMO) of the molecule. The enhancement scales roughly as (wx/w̄ e) 4, where w̄ eis an average excitation energy between the HOMO of the metal and the LUMO of the molecule and w X is the HOMO-LUMO gap of the free molecule. The trend was verified by considering substituted benzenethiols, small molecules, and silver clusters of varying sizes. The results imply that molecules that show significant stabilization of the HOMO-LUMO gaps (such as those that readily accept π-backbonding) would be likely to have strong chemical enhancement. The findings presented here provide the framework for designing new molecules which exhibit high chemical enhancements. However, it remains a challenge to accurately describe the magnitude of the Raman enhancements using electronic structure methods, especially density functional theory, because they often underestimate the energy gap.

Original languageEnglish (US)
Pages (from-to)4090-4098
Number of pages9
JournalJournal of the American Chemical Society
Volume131
Issue number11
DOIs
StatePublished - Mar 25 2009

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Raman Spectrum Analysis
Raman scattering
Metals
Silver
Molecules
Pyridine
Pyridines
Electron energy levels
Density functional theory
Excitation energy
pyridine
Functional groups
Electronic structure
Energy gap
Stabilization

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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abstract = "The enhancement mechanism due to the molecule-surface chemical coupling in surface-enhanced Raman scattering (SERS) has been characterized using time-dependent density functional theory. This has been achieved with a systematical study of the chemical enhancement of meta-and para-substituted pyridines interacting with a small silver cluster (Ag 20). Changing the functional groups on pyridine enabled us to modulate the direct chemical interactions between the pyridine ring and the metal cluster. Surprisingly, we find that the enhancement does not increase as more charge is transferred from the pyridine ring to the cluster. Instead, we find that the magnitude of chemical enhancement is governed to a large extent by the energy difference between the highest occupied energy level (HOMO) of the metal and the lowest unoccupied energy level (LUMO) of the molecule. The enhancement scales roughly as (wx/w̄ e) 4, where w̄ eis an average excitation energy between the HOMO of the metal and the LUMO of the molecule and w X is the HOMO-LUMO gap of the free molecule. The trend was verified by considering substituted benzenethiols, small molecules, and silver clusters of varying sizes. The results imply that molecules that show significant stabilization of the HOMO-LUMO gaps (such as those that readily accept π-backbonding) would be likely to have strong chemical enhancement. The findings presented here provide the framework for designing new molecules which exhibit high chemical enhancements. However, it remains a challenge to accurately describe the magnitude of the Raman enhancements using electronic structure methods, especially density functional theory, because they often underestimate the energy gap.",
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Understanding the molecule-surface chemical coupling in SERS. / Morton, Seth M.; Jensen, Lasse.

In: Journal of the American Chemical Society, Vol. 131, No. 11, 25.03.2009, p. 4090-4098.

Research output: Contribution to journalArticle

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