Calculating dipole and quadrupole polarizabilities relevant to surface enhanced Raman spectroscopy

Gary S. Kedziora, George C Schatz

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

We have used ab initio electronic structure calculations to calculate the frequency dependent dipole-dipole polarizability (α), quadrupole-dipole polarizability (A), quadrupole-quadrupole polarizability (C), (electric) dipole-magnetic dipole polarizability (G), and their normal coordinate derivatives for CO. The polarizability derivatives are of relevance to the interpretation of surface enhanced Raman (SER) spectra. Basis set convergence of these spectroscopic properties is studied, along with the effect of including electron correlation at the second-order polarization propagator (SOPPA) level, and the variation of the results with excitation frequency. The largest basis set SOPPA results that we have generated appear to be converged to within 20% or better for most of the properties we have studied, however in a few cases the convergence is much poorer. The most difficult property to converge involves the off-diagonal component of the derivatives of the quadrupole-dipole polarizability tensor. Our results show that the ratio of the largest components of A to the largest components of α are on the order of one atomic unit in size, and a similar statement can be made concerning the corresponding ratios of the normal coordinate derivatives. This means that the ratio of field derivatives to field strengths will also have to be on the order of one atomic unit in order for A and C to contribute comparably to α in determining SERS intensities.

Original languageEnglish
Pages (from-to)625-638
Number of pages14
JournalSpectrochimica Acta - Part A Molecular and Biomolecular Spectroscopy
Volume55
Issue number3
Publication statusPublished - 1999

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Raman spectroscopy
quadrupoles
dipoles
Derivatives
propagation
Polarization
polarization
Electron correlations
magnetic dipoles
electric dipoles
Carbon Monoxide
field strength
Electronic structure
Tensors
tensors
Raman scattering
Raman spectra
electronic structure
excitation
electrons

Keywords

  • Dipole
  • Quadrupole
  • Raman spectroscopy

ASJC Scopus subject areas

  • Spectroscopy

Cite this

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abstract = "We have used ab initio electronic structure calculations to calculate the frequency dependent dipole-dipole polarizability (α), quadrupole-dipole polarizability (A), quadrupole-quadrupole polarizability (C), (electric) dipole-magnetic dipole polarizability (G), and their normal coordinate derivatives for CO. The polarizability derivatives are of relevance to the interpretation of surface enhanced Raman (SER) spectra. Basis set convergence of these spectroscopic properties is studied, along with the effect of including electron correlation at the second-order polarization propagator (SOPPA) level, and the variation of the results with excitation frequency. The largest basis set SOPPA results that we have generated appear to be converged to within 20{\%} or better for most of the properties we have studied, however in a few cases the convergence is much poorer. The most difficult property to converge involves the off-diagonal component of the derivatives of the quadrupole-dipole polarizability tensor. Our results show that the ratio of the largest components of A to the largest components of α are on the order of one atomic unit in size, and a similar statement can be made concerning the corresponding ratios of the normal coordinate derivatives. This means that the ratio of field derivatives to field strengths will also have to be on the order of one atomic unit in order for A and C to contribute comparably to α in determining SERS intensities.",
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AU - Kedziora, Gary S.

AU - Schatz, George C

PY - 1999

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AB - We have used ab initio electronic structure calculations to calculate the frequency dependent dipole-dipole polarizability (α), quadrupole-dipole polarizability (A), quadrupole-quadrupole polarizability (C), (electric) dipole-magnetic dipole polarizability (G), and their normal coordinate derivatives for CO. The polarizability derivatives are of relevance to the interpretation of surface enhanced Raman (SER) spectra. Basis set convergence of these spectroscopic properties is studied, along with the effect of including electron correlation at the second-order polarization propagator (SOPPA) level, and the variation of the results with excitation frequency. The largest basis set SOPPA results that we have generated appear to be converged to within 20% or better for most of the properties we have studied, however in a few cases the convergence is much poorer. The most difficult property to converge involves the off-diagonal component of the derivatives of the quadrupole-dipole polarizability tensor. Our results show that the ratio of the largest components of A to the largest components of α are on the order of one atomic unit in size, and a similar statement can be made concerning the corresponding ratios of the normal coordinate derivatives. This means that the ratio of field derivatives to field strengths will also have to be on the order of one atomic unit in order for A and C to contribute comparably to α in determining SERS intensities.

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