Hypersensitive Transition of Nd(III) Complexes in Liquids Detected by Pulsed-Laser-Induced Photoacoustic Spectroscopy

Laser-induced photoacoustic (PA) spectroscopy for the spectral measurements of extremely weak absorption such as a forbidden transition of lanthanide ions in liquids has been established. In spectroscopy, a pulsed Nd:YAG laser connected with a MOPO series optical parametric oscillator which emits a broad spectrum covering UV and visible regions is used as the excitation source, and the induced PA signals are detected by an optimized PA piezoelectric transducer. The absorption spectra of trivalent lanthanide ions ( $\text{ Pr}^{3+}, \text{ Ho}^{3+}$ , and $\text{ Nd}^{3+})$ in aqueous solutions have been obtained by the detection system with a detection-limit absorbance of $1.3\times 10^{-5}\,\text{ cm}^{-1}$ at room temperature. In addition, the effects of different binding environments on the band shapes and oscillator strengths of the hypersensitive transitions of $\text{ Nd}^{3+}$ ions, i.e., $\text{ Nd}(\text{ CH}_{3}\text{ COO})_{3}$ $\cdot $ $\text{ H}_{2}\text{ O}$ dissolved in $0.1\,{\text{ mol}} \cdot \text{ l}^{-1}$ acetic acid and $\text{ Nd(3-butanedione)}_{3}{\cdot } 2\text{ H}_{2} \text{ O}$ dissolved in triglycol compared with $\text{ NdCl}_{3}$ in $0.1\,{\text{ mol}}\cdot \text{ l}^{-1}$ hydrochloric acid, are observed. The results show that the chemical environment around the lanthanide ions has great impact on 4f–4f transitions, which is rationalized as the impact in terms of ligand (or solvent) special structures and coordination properties.