An embedded cluster CASPT2 study of the Ce:YVO4 spectrum

Area of Science:

• Computational materials science
• Solid-state chemistry
• Quantum chemistry

Background:

• Accurate electronic structure calculations are crucial for understanding solid materials.
• Describing dopant behavior in host lattices requires sophisticated theoretical methods.

Purpose of the Study:

• To investigate the electronic spectrum of a cerium (Ce(III)) dopant within a YVO4 host material.
• To assess the accuracy and robustness of the multiconfigurational, embedded cluster approach for modeling dopants.

Main Methods:

• Utilized complete active space perturbation theory of the second order (CASPT2).
• Employed an ab initio embedded cluster approach, representing the YVO4 host with model potentials and point charges.
• Evaluated the impact of cluster size and electronic basis set on spectral predictions.

Main Results:

• The CASPT2 method with the embedded cluster approach accurately reproduced the experimental spectrum of Ce(III) in YVO4.
• The computational model demonstrated robustness and sensitivity to cluster and basis set size.
• Low-concentration dopant spectra in complex hosts can be reliably modeled.

Conclusions:

• The embedded cluster approach is a precise and reliable ab initio method for electronic structure calculations of solids.
• This methodology accurately models the spectral properties of low-concentration dopants in complex host materials like YVO4.
• The findings validate the use of advanced quantum chemical methods for materials science applications.