The Cu+ ion impurity in a NaF host has been modeled using a finite cluster of ions to represent the crystal lattice. Several approximations to the lattice potential in the region of the cluster were compared to the exact Madelung potential. The error in the calculated nearest-neighbor distance for the pure host was found to be proportional to the error in the lattice potential. Hartree–Fock calculations were carried out for the ground 1A1g and excited 1,3Eg and 1,3T2g states of the NaF:Cu+ system. The resulting energy level structure was compared to the experimental spectra. The symmetric-stretch potential energy curve, vibrational frequencies, and Franck–Condon factors were calculated for the 1A1g and 1,3T2g states. Using a single configuration coordinate model and a semiempirical spin–orbit coupling scheme, the relative intensities and bandwidths were calculated for absorption to the 1,3T2g states and compared to experiment.
Hartree–Fock cluster calculations have been carried out for the ground 3d10 and excited 3d94s configurations of the Cu+ ion in a NaCl host. Special emphasis has been given to providing an accurate representation of the Coulomb potential due to the remainder of the lattice. Configuration coordinate curves were determined for the symmetric displacement of the nearest-neighbor Cl− ions and are compared to recent Xα calculations. The Hartree–Fock equilibrium Cu–Cl distance was found to be 5.327 bohr, slightly shorter than the calculated nearest-neighbor distance of 5.353 bohr for the pure NaCl host. Comparison of the Hartree–Fock and Xα ground and excited state energies, shows that the Xα approximation reverses the ordering of the 3T2g and 1Eg states, overestimates the equilibrium nearest-neighbor distance, and predicts the a1g vibrational frequency to be about twice the Hartree–Fock value. Using the Franck–Condon factors found with the ab initio potential energy curves, the calculated bandwidths for the 1,3T2g states are found to be in excellent agreement with the low-temperature absorption spectra.
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