Quasi harmonic approximation

Overview

The quasi-harmonic approximation expands upon the harmonic phonon model of lattice dynamics. The harmonic phonon model states that all interatomic forces are purely harmonic, but such a model is inadequate to explain thermal expansion, as the equilibrium distance between atoms in such a model is independent of temperature.

Thus in the quasi-harmonic model, from a phonon point of view, phonon frequencies become volume-dependent in the quasi-harmonic approximation, such that for each volume, the harmonic approximation holds.

Thermodynamics

For a lattice, the Helmholtz free energy F in the quasi-harmonic approximation is

F ( T , V ) = U ( V ) + E Z P ( V ) − T S ( T , V )

where U is the internal lattice energy, E_ZP is the vibrational zero-point energy of the lattice, T is the absolute temperature, V is the volume and S is the entropy due to the vibrational degrees of freedom. The specific definition of the volume is of no particular importance, as long as the definition is used consistently throughout. It can be the volume per primitive unit cell, volume per conventional unit cell, or even molar volume. This choice does not affect the following in any way.

The zero-point energy term equals

E Z P ( V ) = 1 N ∑ k , i 1 2 h ν k , i ( V )

where N is the number of terms in the sum, k is a wave vector, i denotes a phonon band, h is Planck's constant and ν_k,i(V) is the frequency of a phonon with wave vector k in the i-th band at volume V.

The entropy term equals

S ( V ) = − 1 N ∑ k , i k B ln ⁡ [ 1 − exp ⁡ ( − h ν k , i ( V ) k B T ) ] + 1 N ∑ k , i k B h ν k , i ( V ) k B T [ exp ⁡ ( h ν k , i ( V ) k B T ) − 1 ] − 1

where k_B is the Boltzmann constant. The frequency ν as a function of k is the dispersion relation. Note that for a constant value of V, these equations corresponds to that of the harmonic approximation.

By applying a Legendre transform, it is possible to obtain the Gibbs free energy G of the system as a function of temperature and pressure.

G ( T , P ) = min V [ U ( V ) + E Z P ( V ) − T S ( T , V ) + P V ]

Where P is the pressure. The minimal value for G is found at the equilibrium volume for a given T and P.

Derivable quantities

Once the Gibbs free energy is known, many thermodynamic quantities can be determined as first- or second-order derivatives. Below are a few which cannot be determined through the harmonic approximation alone.

Equilibrium volume

V(P,T) is determined as a function of pressure and temperature by minimizing the Gibbs free energy.

Thermal expansion

The volumetric thermal expansion α_V can be derived from V(P,T) as

α V = 1 V ( ∂ V ∂ T ) P

Grüneisen parameter

The Grüneisen parameter γ is defined for every phonon mode as

γ i = − ∂ ln ⁡ ν i ∂ ln ⁡ V

where i indicates a phonon mode. The total Grüneisen parameter is the sum of all γ_is. It is a measure of the anharmonicity of the system and closely related to the thermal expansion.