arXiv subjects

C. W. Li

Publications and source records attributed to C. W. Li.

3 recordsLinked to original sources

arXiv2018

A nuclear quantum effect with pure anharmonicity and the anomalous thermal expansion of silicon

Despite the widespread use of silicon in modern technology, its peculiar thermal expansion is not well-understood. Adapting harmonic phonons to the specific volume at temperature, the quasiharmonic approximation, has become accepted for simulating the thermal expansion, but has given ambiguous interpretations for microscopic mechanisms. To test atomistic mechanisms, we performed inelastic neutron scattering experiments from 100-1500K on a single-crystal of silicon to measure the changes in phonon frequencies. Our state-of-the-art ab initio calculations, which fully account for phonon anharmonicity and nuclear quantum effects, reproduced the measured shifts of individual phonons with temperature, whereas quasiharmonic shifts were mostly of the wrong sign. Surprisingly, the accepted quasiharmonic model was found to predict the thermal expansion owing to a fortuitous cancellation of contributions from individual phonons.

cond-mat.mtrl-sci↗

arXiv2015

Phonon quarticity induced by changes in phonon-tracked hybridization during lattice expansion and its stabilization of rutile TiO$_2$

Although the rutile structure of TiO$_2$ is stable at high temperatures, the conventional quasiharmonic approximation predicts that several acoustic phonons decrease anomalously to zero frequency with thermal expansion, incorrectly predicting a structural collapse at temperatures well below 1000\,K. Inelastic neutron scattering was used to measure the temperature dependence of the phonon density of states (DOS) of rutile TiO$_2$ from 300 to 1373\,K. Surprisingly, these anomalous acoustic phonons were found to increase in frequency with temperature. First-principles calculations showed that with lattice expansion, the potentials for the anomalous acoustic phonons transform from quadratic to quartic, stabilizing the rutile phase at high temperatures. In these modes, the vibrational displacements of adjacent Ti and O atoms cause variations in hybridization of $3d$ electrons of Ti and $2p$ electrons of O atoms. With thermal expansion, the energy variation in this "phonon-tracked hybridization" flattens the bottom of the interatomic potential well between Ti and O atoms, and induces a quarticity in the phonon potential.

cond-mat.mtrl-sci↗

arXiv2013

Phonon self-energy and origin of anomalous neutron scattering spectra in SnTe and PbTe thermoelectrics

The anharmonic lattice dynamics of rock-salt thermoelectric compounds SnTe and PbTe are investigated with inelastic neutron scattering (INS) and first-principles calculations. The experiments show that, surprisingly, although SnTe is closer to the ferroelectric instability, phonon spectra in PbTe exhibit a more anharmonic character. This behavior is reproduced in first-principles calculations of the temperature-dependent phonon self-energy. Our simulations reveal how the nesting of phonon dispersions induces prominent features in the self-energy, which account for the measured INS spectra and their temperature dependence. We establish that the phase-space for three-phonon scattering processes, rather than just the proximity to the lattice instability, is the mechanism determining the complex spectrum of the transverse-optical ferroelectric mode.

cond-mat.mtrl-sci↗