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The Quasi-harmonic (QH) approximation uses harmonic vibrational frequencies omega(H,Q,V), computed at volumes V near the volume where the Born-Oppenheimer (BO) energy is minimum. When this is used in the harmonic free energy, QH…

Materials Science · Physics 2015-08-19 Philip B. Allen

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…

Materials Science · Physics 2015-06-17 Ion Errea , Matteo Calandra , Francesco Mauri

Quantitative evaluations of the free energy of materials must take into account thermal and zero-point energy fluctuations. While these effects can easily be estimated within a harmonic approximation, corrections arising from the anharmonic…

Materials Science · Physics 2019-06-18 Venkat Kapil , Edgar Engel , Mariana Rossi , Michele Ceriotti

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…

We use a hybrid strategy to obtain anharmonic frequency shifts and lifetimes of phonon quasi-particles from first principles molecular dynamics simulations in modest size supercells. This approach is effective irrespective of crystal…

Materials Science · Physics 2015-06-18 Dong-Bo Zhang , Tao Sun , Renata M. Wentzcovitch

Phonon anharmonicity is ubiquitous in real materials and is crucial for understanding thermal properties and phase stability. In this work, we show that anharmonic phonon modes can be obtained by maximizing their vibration stability during…

Materials Science · Physics 2026-05-15 Wenjing Li , Yong Lu , Fawei Zheng

The quasi-harmonic approximation (QHA) is a powerful method that uses the volume dependence of non-interacting phonons to compute the free energy of materials at high pressures (P) and temperatures (T). However, anharmonicity, electronic…

Computational Physics · Physics 2023-08-09 Hongjin Wang , Jingyi Zhuang , Zhen Zhang , Qi Zhang , Renata M. Wentzcovitch

Knowledge of lattice anharmonicity is essential to elucidate distinctive thermal properties in crystalline solids. Yet, accurate \textit{ab initio} investigations of lattice anharmonicity encounter difficulties owing to the cumbersome…

Materials Science · Physics 2022-04-13 Zhen Zhang , Dong-Bo Zhang , Tao Sun , Renata M. Wentzcovitch

We formulate a theory of thermal expansion based on the self-consistent phonon (SCP) theory, which nonperturbatively considers the anharmonic effect. We show that the Gr\"unseisen formula holds within the SCP theory by replacing the phonon…

Materials Science · Physics 2022-12-20 Ryota Masuki , Takuya Nomoto , Ryotaro Arita , Terumasa Tadano

Phonon-phonon anharmonic effects have a strong influence on the phonon spectrum; most prominent manifestation of these effects are the softening (shift in frequency) and broadening (change in FWHM) of the phonon modes at finite temperature.…

To address the effects of lattice anharmonicity across the perovskite to post-perovskite transition in MgSiO$_3$, we conduct calculations using the phonon quasiparticle (PHQ) approach. The PHQ is based on \textit{ab initio} molecular…

Materials Science · Physics 2022-12-05 Zhen Zhang , Renata M. Wentzcovitch

Effective harmonic methods allow for calculating temperature dependent phonon frequencies by incorporating the anharmonic contributions into an effective harmonic Hamiltonian. The systematic errors arising from such an approximation are…

Materials Science · Physics 2019-06-05 Erki Metsanurk , Mattias Klintenberg

Phonons, quantized vibrations of the atomic lattice, are fundamental to understanding thermal transport, structural stability, and phase behavior in crystalline solids. Despite advances in computational materials science, most predictions…

Materials Science · Physics 2026-01-15 Huiju Lee , Zhi Li , Jiangang he , Yi Xia

The efficient and accurate calculation of how ionic quantum and thermal fluctuations impact the free energy of a crystal, its atomic structure, and phonon spectrum is one of the main challenges of solid state physics, especially when strong…

Anharmonic lattice vibrations govern the thermal dynamics in materials and present how the atoms interact and how they conduct heat. An indepth understanding of the microscopic mechanism of phonon anharmonicity in condensed systems is…

Materials Science · Physics 2021-12-30 Bin Wei , Qiyang Sun , Chen Li , Jiawang Hong

We propose a method to evaluate the Gibbs free energy from constant-volume first-principles phonon calculations. The volume integral of the pressure is performed by determining the volume and the bulk modulus in equilibrium at finite…

Materials Science · Physics 2025-07-02 Kota Hashimoto , Tomonori Tanaka , Yoshihiro Gohda

The phonon Casimir effect describes the phonon-mediated interaction between defects in condensed-matter systems. Using the path-integral formalism, we derive a general method for calculating the Helmholtz free energy due to vibrational…

Mesoscale and Nanoscale Physics · Physics 2021-06-02 Gideon Lee , Aleksandr Rodin

While the vibrational thermodynamics of materials with small anharmonicity at low temperatures has been understood well based on the harmonic phonons approximation; at high temperatures, this understanding must accommodate how phonons…

Materials Science · Physics 2015-10-20 Tian Lan

The quasiharmonic approximation is the most common method for modeling the specific heat of solids; however, it fails to capture the effects of intrinsic anharmonicity. In this study, we introduce the "elastic softening approximation," an…

With a study of bulk GaAs and GaP, we report detailed infrared spectra and their temperature dependence from first principles. Fine features and low-temperature trends in the predicted response are confirmed by experiment. The spectra are…

Materials Science · Physics 2007-05-23 Hadley M. Lawler , Eric L. Shirley
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