Anharmonic free energies and phonon dispersions from the stochastic self-consistent harmonic approximation: Application to platinum and palladium hydrides

By I. Errea, M. Calandra, F. Mauri. 2013

308 citations recorded by the source corpus.

Harmonic calculations based on density-functional theory are generally the method of choice for the description of phonon spectra of metals and insulators. The inclusion of anharmonic effects is, however, delicate as it relies on perturbation theory requiring a considerable amount of computer time, fast increasing with the cell size. Furthermore, perturbation theory breaks down when the harmonic solution is dynamically unstable or the anharmonic correction of the phonon energies is larger than the harmonic frequencies themselves. We present here a stochastic implementation of the self-consistent harmonic approximation valid to treat anharmonicity at any temperature in the nonperturbative regime. The method is based on the minimization of the free energy with respect to a trial density matrix described by an arbitrary harmonic Hamiltonian. The minimization is performed with respect to all the free parameters in the trial harmonic Hamiltonian, namely, equilibrium positions, phonon frequencies, and polarization vectors. The gradient of the free energy is calculated following a stochastic procedure. The method can be used to calculate thermodynamic properties, dynamical properties, and even anharmonic corrections to the Eliashberg function of the electron-phonon coupling. The scaling with the system size is greatly improved with respect to perturbation theory. The validity of the method is demonstrated in the strongly anharmonic palladium and platinum hydrides. In both cases, we predict a strong anharmonic correction to the harmonic phonon spectra, far beyond the perturbative limit. In palladium hydrides, we calculate thermodynamic properties beyond the quasiharmonic approximation, while in PtH, we demonstrate that the high superconducting critical temperatures at 100 GPa predicted in previous calculations based on the harmonic approximation are strongly suppressed when anharmonic effects are included.

Subfields: Atomic and Molecular Physics, and Optics, Condensed Matter Physics, Geophysics

View Paper: https://www.semanticscholar.org/paper/cf4420fb6983a4fa373cae05d78df22668aebf0e

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In Atomic and Molecular Physics, and Optics

1. Isao Tanaka
2. Atsushi Togo
3. J. A. Flores-Livas
4. Ryotaro Arita
5. M. Eremets
6. G. Profeta
7. A. Sanna
8. L. Boeri

In Condensed Matter Physics

1. J. A. Flores-Livas
2. Ryotaro Arita
3. M. Eremets
4. G. Profeta
5. Isao Tanaka
6. A. Sanna
7. L. Boeri
8. Atsushi Togo

In Geophysics

1. Isao Tanaka
2. Atsushi Togo
3. J. A. Flores-Livas
4. Ryotaro Arita
5. M. Eremets
6. G. Profeta
7. A. Sanna
8. L. Boeri

Citations in the corpus

• First principles phonon calculations in materials science (2015, methodology): “arge atomic displacements can stabilize the BCC structure. In such a case, the perturbation approach is invalid. Phonons with large atomic displacements may be treated by self-consistent phonon method[25, 36] or by a combination of molecular dynamics and lattice dynamics calculation[37, 38, 39], whi”
• A perspective on conventional high-temperature superconductors at high pressure: Methods and materials (2019, methodology): “This problem has been recently tackled by ErreaCalandra-Mauri by introducing a stochastic approach to sample the energy surface [208, 223].”