First-Principles Study of the Electronic, Vibrational Properties and Anharmonic Effects of Some Si-Based Type-II Binary Clathrates.

Electronic, vibrational, and anharmonic studies on some binary clathrate ASi (A = Na, K, Rb, Cs; 0 < ≤ 24) are theoretically presented. The Fermi energy lies in the range of 1.1 eV to 1.4 eV for NaSi and increases as stoichiometry () is tuned from 8 to 12 to 16. The determined isotropic "Mexican-hat" shape of the guest-host potential describing Na motion in the Si cage indicates the "off-center" position when the temperature is elevated beyond zero. Accordingly, the calculated Na "off-center" displacements correlate well with the X-Ray Diffraction (XRD) data (0.4 Å⁻0.5 Å) for a similar composition range (0 < < 24). The lack of first-principles analysis on quartic anharmonicity motivates us to initiate a self-consistent model to examine the temperature-dependent rattling frequency () of the guest (Na, Rb). The predicted values of () for NaSi at 300 K are significantly higher (approximately six times larger) than the value at absolute zero, which contrasts with the case of Rb₈Si. Moreover, underestimation of the isotropic atomic displacement parameter is caused by the temperature-dependent quartic anharmonicity of Na, and this discrepancy might be offset by the square of the "off-center" displacement.