pH Dependent surface enhanced Raman study of Phe + Ag Complex and DFT calculations for spectral analysis

TL;DR

This study investigates how pH influences the surface-enhanced Raman spectra of phenylalanine-Ag complexes, revealing mechanisms behind spectral changes and supporting findings with DFT calculations.

Contribution

It provides new insights into pH-dependent spectral behavior of phenylalanine-Ag complexes using SERS and DFT, highlighting charge state effects and spectral line-shape analysis.

Findings

Spectral line-width varies with pH, indicating fluctuation or motional narrowing mechanisms.

Different charge states of phenylalanine affect bond softening at varying pH levels.

DFT calculations successfully explain the observed Raman shifts and activity.

Abstract

Surface enhanced Raman spectra of Phenylalanine (Phe) in Ag colloidal solution have been recorded for Phe solutions of different pH. Spectral line-shape analyses of the enhanced modes, at 1005, 1380 and 1582 cm-1, between pH 4.5 and 10.5, have been carried out. The variation of spectral line-width with pH reveals two possible mechanisms in solution: (i) the fluctuation of pH in microscopic volume in an overall uniform pH solution and/or (ii) the motional narrowing caused by the intermolecular ionic interaction. We suggest that different charge states of the reference molecule are responsible for the observed bond softening with decrease in pH. The observed Raman shift and the Raman activity of the vibrational modes with maximum enhancement have been explained by carrying out DFT calculations.