Theoretical Vibrational Raman and Surface‐Enhanced Raman Scattering Spectra of Water Interacting with Silver Clusters. Issue 18 (26th September 2014)

• Record Type: Journal Article
• Authors: Sanchéz‐Lozano, Marta; Mandado, Marcos; Pérez‐Juste, Ignacio; Hermida‐Ramón, Jose M.
• Is Part Of: Chemphyschem. Volume 15:Issue 18(2014)
• Page Start: 4067
• Page End: 4076
• Publication Date: 2014-09-26
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.05
• DOI: 10.1002/cphc.201402454
• Languages: English
• ISSNs: 1439-4235

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>In this study, we analyzed the Raman spectrum of a water molecule adsorbed on a cluster of 20 silver atoms, and the plasmonic electromagnetic effect of the silver surface was also considered to give a theoretical prediction of the surface‐enhanced Raman scattering spectrum. The calculations were performed at the density functional theory (DFT) level by using both frozen and unfrozen silver clusters. Two different models were used to consider the plasmonic enhancement; one of them was a modified classical (dipole) model and the other was the coupled perturbed Hartree–Fock method with excitation frequencies obtained from time‐dependent DFT calculations and with proper detuning of these frequencies. The importance of small geometrical distortions of the silver surface in the orientation of the adsorbed water was shown. Moreover, it was shown how the symmetry of the transition dipole moment and the symmetry of the vibrational modes influence the Raman intensities of the SERS spectrum.</p> </abstract>