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arXiv · 2503.17800

Surface-enhanced Raman scattering and density functional theory study of selected-lanthanide-citrate complexes (lanthanide: La, Ce, Pr, Nd, Sm, Eu, and Gd)

Hao Jin·Tamitake Itoh·Yuko S. Yamamoto
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Abstract

In this study, we combined the surface-enhanced Raman scattering (SERS) with density functional theory (DFT) calculations to investigate the SERS spectra of lanthanide (Ln)-citrate complexes (Ln = La, Ce, Pr, Nd, Sm, Eu, and Gd) under 488, 532, and 660 nm laser excitations. Detailed vibrational analysis and peak assignments were performed based on SERS spectra simulated using an optimized DFT setting, in which small-core effective core potentials (ECPs) in the def2-tzvpd basis set were replaced by large-core ECPs. Characteristic SERS peaks appeared at 1065, 1315, and 1485 cm-1 were assigned to the γ(CH2)+v(C-O{\ldots}Ln), vsym(COO-)+γ(CH2), and vasym(COO-)+γ(CH2) vibrational bands, respectively. SERS intensity ratios were obtained by normalizing the peak intensity I near 1065 or 1485 cm-1 to that near 1315 cm-1. I1065/I1315 depended solely on the type of Ln3+ ion and was independent of the excitation wavelength. In contrast, I1485/I1315 increased with decreasing excitation wavelength, indicating additional enhancement by charge-transfer. Additionally, as the number of unpaired 4f electrons increased, Ln3+ in the coordination region attracted oxygen negative charges more strongly, reducing the electric dipole moment of the C-O bond and altering its symmetry.

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Hao Jin, Tamitake Itoh, Yuko S. Yamamoto. 2025-03-22. Surface-enhanced Raman scattering and density functional theory study of selected-lanthanide-citrate complexes (lanthanide: La, Ce, Pr, Nd, Sm, Eu, and Gd). https://arxiv.org/abs/2503.17800

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