An introduction to linear response

and to phonon calculations

P. Giannozzi
Università di Udine and IOM-Democritos, Trieste

March 28, 2018

Reference: Phonons and related crystal properties from density-functional

perturbation theory, S. Baroni, S. de Gironcoli, A. Dal Corso, and P. Giannozzi,
Rev. Mod. Phys. 73, 515-562 (2001).

– Typeset by FoilTEX –
 Electronic screening
Consider a static perturbation δV0(r) to a system of electrons under an external
(nuclear) potential V0(r). At linear order,
Z
δn(r) = χ(r, r0)δV0(r0)dr0

where χ(r, r0) is the density response of the system.

The polarization charge δn(r) produces an electrostatic field that screens the
perturbing potential δV0(r):

δn(r0) 0
Z
2
δV (r) = δV0(r) + e 0
dr
|r − r |

that is:
Z  00 0
Z  Z
χ(r , r ) 00
δV (r) = δ(r − r0) + e2 dr δV0 (r 0
)dr 0
≡ −1(r, r0)δV0(r0)dr0.
|r − r00|

−1(r, r0) is the dielectric response function as usually defined in electrostatics.

 Linear Response functions

• χ(r, r0)
yields the charge response to a bare (external) perturbing potential via
Z
δn(r) = χ(r, r0)δV0(r0)dr0

• −1(r, r0)
yields the screened potential from the bare one via
Z
δV (r) = −1(r, r0)δV0(r0)dr0.

and is related to χ(r, r0) via

χ(r00, r0) 00
Z
−1 0 0 2
 (r, r ) ≡ δ(r − r ) + e 00
dr
|r − r |

These are the functions that determine electronic response. Their calculation is
however a nontrivial many-body problem.
 Density-Functional Linear Response
We assume that the system obeys Kohn-Sham (KS) equations:

h̄2 2
(HKS − i) ψi(r) = 0, HKS = − ∇ + VKS (r)
2m
where VKS (r) = V0(r) + VH (r) + Vxc[n(r)] and the charge is given by
X
n(r) = fi|ψi(r)|2
i

(general case of noninteger occupancy fi).

Let us add an external δV0(r) to V0(r): the potential VKS will be modified by
δVKS = δV0(r) + δVH (r) + δVxc[n(r)]. Let us consider first order (linear response).
We introduce the independent-particle polarizability χ0(r, r0) via
Z
δn(r) = χ0(r, r0)δVKS (r0)dr0.

Unlike χ(r, r0), this quantity can be easily calculated using perturbation theory.
 Independent-particle polarizability

The first-order variation of KS orbitals:

X hψj |δVKS |ψii
δψi(r) = ψj (r)
i − j
j6=i

and of the charge density (after some manipulations):

X X fi − fj
δn(r) = fiδψi∗(r)ψi(r) + c.c. = ψi∗(r)ψj (r)hψj |δVKS |ψii
i
i − j
i,j,i6=j

Note that contribution from i, j states vanishes if both are fully occupied. For a
closed-shell (insulating) system:

X
∗ hψc|δVKS |ψv i
δn(r) = 4Re ψv (r)ψc(r)
v,c
v − c

v = filled (valence) states, c = empty (conduction) states, a factor 2 from spin.

 Independent-particle polarizability II

We can write the independent-particle polarizability χ0(r, r0) as

X ψ ∗(r)ψc(r)ψ ∗(r0)ψv (r0)

0 v c
χ0(r, r ) = 4Re .
v,c
v − c

which can be recast into the form

0
X 1
χ0(r, r ) = 4Re ψv∗(r)Pc Pcψv (r0)
v
v − HKS

where Pc is the projector operator over conduction states.

Note that:

• this expression is valid only if VKS ≡ VKS (r), i.e. is a local potential:

• χ0(r, r0) is a ground-state property: it yields the difference between two ground
states, even if it seems to depend on excited-state energies c
 Physical Response Operator
...but we need χ(r, r0), not χ0(r, r0) ! How can we get from χ0 to χ ?
In operator notations: δn = χ̂δV0 = χ̂0δVKS , and δVKS = δV0 +δVH +δVXC .
Screening from Hartree potential:
Z 0 2
δn(r ) 0 e
δVH (r) = e 2
dr ≡ v̂cδn, where vc(r, r0) =
|r − r0| |r − r0|

Screening from exchange-correlation:

Z
δVxc(r)
δVxc(r) = fxc(r, r0)δn(r0)dr0 ≡ fˆxcδn, where 0
fxc(r, r ) =
δn(r0)

After some algebra (remember that these are operators!):

χ̂ = χ̂0 + χ̂0(v̂c + fˆxc)χ̂

and finally  −1

χ̂ = χ̂−1 ˆ
0 − v̂c − fxc
 Physical Response Operator in practice

Major problem: how to invert the operators!

In solids, the response function χ0(r, r0) can be expressed in reciprocal space as a
matrix, the dielectric matrix: χ0(q + G, q + G0), for the response to an external
perturbation of wavevector q. Operators become infinite matrix. By truncating
them at an appropriate Gcut one has a practical scheme for calculating response
operators.

Local-field effects: those due to the presence of G 6= 0 terms.

Random Phase Approximation (RPA): neglect the fxc term. Note that the addition
of LDA exchange-correlation is straightforward: fxc is a local operator

0 0 dVxc (n) 

fxc(r, r ) = δ(r − r ) .
dn n=n(r)

The dielectric matrix approach yields the response to all possible perturbations,
but only local ones (i.e. δV local), and is computationally heavy. However we are
often interested to the response to a specific and/or nonlocal perturbation.
 Self-consistent Linear Response
We consider the basic equations, to be self-consistently solved:

δVKS = δV0 + v̂cδn + fˆxcδn

and
X hψc|δVKS |ψv i X 1
δn(r) = 4Re ψv∗(r)ψc(r) = 4Re ψv∗(r)Pc PcδVKS ψv .
v,c
v − c v
v − HKS

The variation of the charge density can be recast into the form
X 1
δn(r) = 4Re ψv∗(r)∆ψv (r), where ∆ψv = Pc PcδVKS ψv
v
v − HKS

∆ψv can be obtained from the solution of a linear equation:

(v − HKS ) Pc∆ψv = PcδVKS ψv .

The above equations define a self-consistent procedure that can be solved by

iteration, much in the same way as in the solution of KS equations.
 Linear Response to an Electric Field
If the perturbing potential represents a macroscopic electric field δE:

δV0 = −eδE0 · r

it is ill-defined in a crystal, because r is not a lattice-periodic operator! it can

however be recast into a well-defined expression using the following trick:

hψc|[HKS , r]|ψv i
hψc|r|ψv i = for c 6= v.
c − v

We can rewrite |ψ̄vαi = Pcrα|ψv i as the solution of a linear system:

(HKS − v )|ψ̄vαi = Pc[HKS , rα]|ψv i,

where the commutator can be calculated from the following expression:

h̄2 ∂ h i
[HKS , r] = − + V̂N L, r .
m ∂r
(VN L is the nonlocal term of the potential if present).
 Macroscopic Polarization

The bare macroscopic electric field will be screened according to electrostatic:

Eα α,β
P
0 = β ∞ Eβ , where ∞ is the electronic (clamped-nuclei) contribution to the
dielectric tensor. This is related to the induced polarization P via E0 = E + 4πP
so that
δPα
α,β
∞ = δ α,β + 4π
δEβ
The macroscopic induced polarization can be calculated as
Z
e e X
α 
δPα = − rαδn(r)dr = ψ̄v |∆ψv .
NcΩ NcΩ v

(Nc is the number of cells of volume Ωc, NcΩ is the crystal volume) using the
same trick as shown before. In practical calculations, the (screened) electric field
E is kept fixed, iteration is performed on the microscopic terms of the potential:
Z  2

e δvxc(r) 0
δVKS (r) = −eδEαrα + 0
+ 0
δn(r ).
|r − r | δn(r )
 Linear Response and Phonons

An important advantage of the self-consistent approach to Linear Response: the

typical PW-PP technology can be straightforwardly applied. Note that the projector
over empty states can be written as
X
Pc = 1 − Pv = 1 − |ψv ihψv |
v

so that conduction bands are never explicitly required.

Typical application: calculation of normal vibrational modes, and especially phonons

in crystals. The ”perturbing potential” is in this case the displacement of a nuclear
potential (or of a group of them). Once δn(r) is (are) calculated, the dynamical
matrix can be easily derived, along with phonon modes and frequencies. To this
end, we need to know the form of the second-order expansion term of the energy.

Such procedure is often called Density-Functional Perturbation Theory (DFPT).

(in the following, notations change: derivatives replace infinitesimal increments)

 Density-Functional Perturbation Theory
Let us assume that the external potential depends on some parameter λ

∂V (r) 1 2 ∂ 2V (r)
Vλ(r) ' V (r) + λ + λ 2
+ ...
∂λ 2 ∂λ
(all derivatives calculated at λ = 0) and expand the charge density

∂n(r) 1 2 ∂ 2n(r)
nλ(r) ' n(r) + λ + λ + ...
∂λ 2 ∂λ2
and the energy functional into powers of λ:

∂E 1 2 ∂ 2E
Eλ ' E + λ + λ + ...
∂λ 2 ∂λ2
The first-order derivative ∂E/∂λ does not depend on any derivative of n(r)
(Hellmann-Feynman theorem):
Z
∂E ∂V (r)
= n(r) dr
∂λ ∂λ
 Energy functional expansion terms

The second-order derivative ∂ 2E/∂λ2 depends on the first-order derivative of the

charge density, ∂n(r)/∂λ:

∂ 2E ∂ 2V (r)
Z Z
∂V (r) ∂n(r)
= dr + n(r) dr
∂λ2 ∂λ ∂λ ∂λ2

The result can be generalized to mixed derivatives:

∂ 2E ∂ 2V (r)
Z Z
∂V (r) ∂n(r)
= dr + n(r) dr
∂λ∂µ ∂λ ∂µ ∂λ∂µ

(the order of derivatives can be exchanged)

In general, the (2n + 1)−th derivative of energy depends only on derivatives up to

order n of the charge density ((2n + 1) theorem) due to its variational character.

∂n/∂λ can be calculated either by the self-consistent procedure shown above, or

by direct minimization of the 2nd-order energy, written as a functional of ∂n/∂λ.
 Born-Oppenheimer approximation

The behavior of a system of interacting electrons r and nuclei R is determined by

the solutions of the time-dependent Schrödinger equation:
!
2
X h̄ ∂ 2 X h̄ ∂ 2 2
∂ Φ̂(r, R; t)
ih̄ = − 2 − 2 + V (r, R) Φ̂(r, R; t)
∂t 2MI ∂RI i
2m ∂ri
I

where V (r, R) is the potential describing the coulombian interactions:

X Z i Z J e2 X Z I e2 X e2
V (r, R) = − +
|RI − RJ | |ri − RI | i>j |ri − rj |
I>J i,I

≡ Vnn(R) + Vne(r, R) + Vee(r)

Born-Oppenheimer (or adiabatic) approximation (valid for MI >> m):

Φ̂(r, R; t) ' Φ(R)Ψ(r|R)e−iÊt/h̄

NB: r ≡ (r1, .., rN ), R ≡ (R1, .., Rn)

 Potential Energy Surface

The Born-Oppenheimer approximation allows to split the problem into an electronic

problem depending upon nuclear positions:
!
X h̄ ∂2 2
− 2 + V (r, R) Ψ(r|R) = E(R)Ψ(r|R)
i
2m ∂r i

and a nuclear problem under an effective interatomic potential determined by the

electrons: !
2
X h̄ ∂ 2
− + E(R) Φ(R) = ÊΦ(R)
2MI ∂R2i
I
E(R) determines the Potential Energy Surface and the equilibrium geometry. At
equilibrium, forces FI on nuclei vanish:

∂E(R)
FI = − =0
∂RI

NB: r ≡ (r1, .., rN ), R ≡ (R1, .., Rn)

 Normal vibrational modes in crystals and molecules
Harmonic approximation: the interatomic potential energy is expanded to 2nd
order. The resulting Hamiltonian transforms into a sum of independent oscillators.
Normal mode frequencies, ω, and displacement patterns, UIα for cartesian
component α of atom I, at atomic position RI , are determined by the secular
equation: X  αβ 
CIJ − MI ω δIJ δαβ UJβ = 0,
2

J,β
αβ
where CIJ is the matrix of inter-atomic force constants (IFC), i.e. second
derivatives of the energy with respect to atomic positions:

αβ ∂ 2E({R})
CIJ ≡ .
∂RIα∂RJβ

In crystals, normal modes are classified by a wave-vector q. Phonon frequencies,

ω(q), and displacement patterns, Usα(q), are determined by the secular equation:
X  αβ 
Cest (q) − Msω 2(q)δstδαβ Utβ (q) = 0
t,β
 Calculation of phonon spectra
Introduce monochromatic perturbation u to atomic positions RI = Rl + τ s as

RI [us(q)] = Rl + τ s + us(q)eiq·Rl .

(Rl =lattice vector, τ s =equilibrium position of the s-th atom in the unit cell).
Fourier transform of force constants at q are second derivatives of the energy with
respect to such monochromatic perturbations:

αβ
X
−iq·R αβ 1 ∂ 2E
C
est (q) ≡ e Cst (R) = β
Nc ∂u∗α
s (q)∂u t (q)
R

This can be calculated from the knowledge of the linear response ∂n(r)/∂uα
s (q)
and diagonalized to get phonon modes at q. Note that:

• the linear response has the same wave vector q of the perturbation: this
algorithm will work for any q without any supercell involved

• in the spirit of adiabatic approximation, one can use static response.

 Frozen phonon

Frozen phonons is an older and alternative way to calculate phonons. The

monochromatic perturbation is frozen in with a finite amplitude in the system,
which is described by a supercell having q as reciprocal lattice vector.

Fourier transform of force constants at q are calculated from finite differences of

forces induced on all the atoms of the supercell by the monochromatic perturbation.

Advantages:

• straightforward to implement

Disadvantages:

• limited to small supercells, i.e. q = G/n, where G is a reciprocal lattice vector

of the original cell, n = 2, 3, 4, ..., but in any case a small number.

Note that this is not the algorithm used by quantum ESPRESSO!

What if we want the entire dispersions for all q-vectors in the Brillouin Zone?
 Phonons and macroscopic electric fields

Polar materials in the q=0 (long-wavelength) limit: a macroscopic (finite and

constant) electric field is present. Gives raise to observable TO-LO splitting.
Macroscopic electric field incompatible with Periodic Boundary Conditions! Must
be separately treated.

Phenomenological expression for the energy as a function of atomic displacements,

us, and of macroscopic electric field, E (Born and Huang long-wavelength limit):

1 XX ane Ω X
E({u}, E) = us · Cst · ut − E · ∞ · E − e us · Z?s · E,
2 st 8π s
αβ

(anC
e st force constants, ∞ dielectric tensor, Z?s Born effective charge tensor).

Under which circumstances is an electric field E generated by atomic displacements

u? Which consequences does it have? The answer comes from electrostatics.
 Phonons and macroscopic electric fields (2)

Let us consider electric induction D = E + 4πP (where P is the polarization):

4π X
D = E + Pel + Pion = ∞ · E + e us · Z?s
Ω s

Maxwell equations tell us q · D = 0 and q × E = 0 =⇒ E = q(q · E), hence

4πe X q(q · Z?tut)

E=−
Ω t q · ∞ · q

and
1 XX e st = anC
e st + naC
E({u}) = us · C
e st · ut, C e st
2 st
αβ
where ? ?
nae 4π (q · Z s )α (q · Z t )β
Cst =
Ω q · ∞ · q
A ”non-analytical” term has appeared in the force constants!
 Effective charges and dielectric tensor
Effective charges Z? are related to polarization P induced by a lattice distortion:
Ω ∂Pα
Z ?αβ
s = β
.
e ∂us (q = 0)

Dielectric tensor αβ

∞ are related to polarization induced by an electric field E:

αβ ∂Pα 
∞ = δαβ + 4π .
∂Eβ us(q=0)=0

One can observe that such quantities are second derivatives of the energy as well:

1 ∂ 2E
Z ?αβ
s = Zsδαβ − β
,
Nc ∂Eα∂us (q = 0)

(Nc number of cells in crystal)

1 ∂ 2E
αβ
∞ = δαβ + .
Nc ∂Eα∂Eβ
 Calculation of effective charges

Polarization induced by an atomic displacement:

Z
∂Pα e ∂n(r) e
β
=− r dr + Zsδαβ .
∂us (q = 0) NcΩ ∂us(q = 0) Ω

Integral is ill-defined for a crystal with Periodic Boundary Conditions! Can use a
trick:
hψm|[HSCF , r]|ψni
hψm|r|ψni = , ∀ m 6= n
m − n
(in fact, only non-diagonal matrix elements are needed). The commutator is well
defined:
h̄2 ∂
[HSCF , r] = − + [VN L, r]
m ∂r
(momentum operator, plus a contribution from nonlocal pseudopotentials). Let us
define |ψ̄nαi = rα|ψni the solution of linear system:

(HSCF − n)|ψ̄nαi = Pc[HSCF , rα]|ψni

(Pc is the projector over condution states).

 Calculation of effective charges (2)

Effective charges are then given by:

N/2   
4 X ∂ψn
Z ?αβ ψ̄nα 

s = Zs + .
Nc n=1 ∂uβ (q = 0)

using the linear response to an atomic perturbation.

Alternatively, effective charges are given by the force linearly induced on an atom
by an electric field:

N/2   
4 X ∂V ∂ψn
Z ?αβ
 
s = Zs + ψn 
  .
Nc n=1 ∂uβ (q = 0)  ∂Eα

using the linear response to an electric field (this is so because the Z ? are mixed
second derivatives of the energy). quantum ESPRESSO can do both types of
calculations (they yield the same result within numerical accuracy!)
 Calculation of dielectric tensor

The linear response to a macroscopic electric field can be calculated using the same
trick as above. In fact, V (r) = eE · r is ill-defined but we need only non-diagonal
matrix elements. The convenient way to solve the linear-response equations is to
iterate over VSCF (r) while keeping E fixed:

2
∂n(r0) 0
Z  
∂VSCF (r) ∂V (r) e δvxc(r)
= + + dr .
∂E ∂E |r − r0| δn(r0) ∂E

Finally:
N/2   
16πe X ∂ψn
αβ ψ̄nα 

∞ = δαβ − .
NcΩ n=1
∂Eβ
In the end, all we need to properly deal with LO-TO splitting in phonons are three
additional linear-response calculations to an electric field

Final note: alternative techniques based on the modern theory of polarizability

(Berry’s phase) exist for the calculation of effective charges (also implemented in
quantum ESPRESSO)
 Inter-atomic force constants in real space

αβ
Inter-atomic force constants in real space, Cst (R), are obtained by

αβ
• calculating C
est (q) on a discrete (n1, n2, n3) grid of q-vectors:

i−1 j−1 k−1

qijk = G1 + G2 + G3, i = 1, .., n1, and the like for j, k;
n1 n2 n3

• Fourier-transforming to the corresponding real-space grid:

C(qijk ) ⇐⇒ C(Rlmn), Rlmn = lR1 + mR2 + nR3

l = −n1/2, ..., n1/2 and the like for m, n.

The denser the grid of q-vectors, the larger the vectors Rlmn for which the
inter-atomic force constants are calculated. For non polar system, inter-atomic
force constants are short-ranged and require a moderate number of calculations at
different q.
 Inter-atomic force constants in real space (2)

In simple semiconductors like Si and Ge, q-point grids like 4 × 4 × 4 already yield
rather converged force constants in real space. Symmetry is used to reduce the
number of needed linear-response calculations.

Once inter-atomic force constants are known, the entire phonon dispersion at any
q can be straightforwardly calculated.

References: Phonons and related crystal properties from density-functional

perturbation theory, S. Baroni, S. de Gironcoli, A. Dal Corso, and P. Giannozzi,
Rev. Mod. Phys. 73, 515-562 (2001).

Density-Functional Perturbation Theory, P. Giannozzi and S. Baroni, in Handbook

of Materials Modeling, Vol.1: “Methods and Models”, Editor S. Yip, Volume
Editors: E. Kaxiras, N. Marzari, and B. Trout (Springer, 2005), p.195-214

Thermal Properties of Materials from ab-initio Quasi-Harmonic Phonons, S. Baroni,

P. Giannozzi, and E. Isaev, Rev. Mineral. Geochem. 71, 39-57 (2010)
 Interatomic force constants in polar materials

For materials having a TO-LO splitting (e.g.: polar semiconductors), the non-
analytic term in the force constants makes inter-atomic force constants in real
space no longer short-ranged. Fourier-interpolation is no longer possible. Solution:

αβ
• Subtract from C est (qijk ) a term that has the same q → 0 limit of the non-
αβ
analytic term naCest (q) (and that is easy to calculate)

• Fourier-transform from reciprocal to real space as for the non-polar case: force
constants in real space are now short-ranged.

• When force constants at a general q are re-calculated from those in real space,
re-add the term removed before the Fourier transform.

quantum ESPRESSO uses the same term as the one described in:
X. Gonze et al., Phys. Rev B 50, 13035 (1994)
 Calculation of IR and Raman Intensities

Infrared Intensities:  2

X X αβ 
? β

IIR(ν) = 
 Z s Us (ν)
α  sβ 
can be calculated directly from effective charges and phonon displacement patterns.

Non-resonant Raman intensities:

4  ∂χαβ 2
 
(ωi − ων )
IStokes(ν) ∝ rαβ (ν), rαβ (ν) =  
ων ∂U (ν) 

where χ is the electric polarizability of the system.

Raman coefficients are third-order derivatives of the energy that can be calculated
in various ways. The most convenient way is to use second-order response to
an electric field: M.Lazzeri and F.Mauri, Phys. Rev. Lett. 90, 036401 (2003).
Implemented (but not for USPP or PAW) in quantum ESPRESSO.
 Superconducting Tc and electron-phonon interaction

Electron-phonon interaction λ:
X X γ qν
λ= λ qν =
qν qν
πh̄N (F )ωq2ν

where N (F ) is the DOS at the Fermi level, and for phonon mode ν at wavevector
q:
X Z d3 k
γqν = 2πωqν |gqν (k, i, j)|2δ(q,i − F )δ(k+q,j − F ),
ij
ΩBZ
 1/2
h̄ ∂VSCF
gqν (k, i, j) = hψi,k| (ν) |ψj,k+qi.
2M ωqν ∂U (q)
U (ν) is a displacement along phonon ν. This quantity can be easily calculated
using DFPT. McMillan formula for Tc:
 
ΘD −1.04(1 + λ)
Tc = exp
1.45 λ(1 − 0.62µ∗) − µ∗
 Practical phonon calculation in quantum ESPRESSO

First step: scf calculation at equilibrium positions (performed by pw.x)

• Single phonon calculation at finite wave-vector q

– Generate ψk,v and ψk+q,v in the Irreducible Brillouin Zone relative to the
small group of q; Calculate C(q), diagonalize, produce ω(q) and U (q) (code
ph.x)

• Single phonon calculation at Γ wave-vector (q=0)

– Calculate C(q = 0), diagonalize, produce ω(q = 0) and U (q = 0) (code
ph.x)
For polar materials: calculate non-analytical terms that are missing from
C(q = 0) (LO-TO splitting are absent from ω(q = 0)): specify option
epsil=.true. to ph.x (will calculate and store in output file Z ∗ and ∞).
– Impose Acoustic Sum Rule (ASR), add the nonanalytic LO-TO splitting,
calculate cross sections (code dynmat.x)

Sample input files in examples phon.tar.gz

 Practical phonon dispersions calculation
First step as before: scf calculation at equilibrium positions (performed by pw.x)

• Perform many single-phonon calculations on a uniform grid of wave-vectors qi,

including q = 0 (if system is polar, calculate in the latter case Z ∗ and ∞); save
all C(qi) (and Z ∗, ∞) (code ph.x with option ldisp=.true.)

• Perform inverse FFT of the C(qi), obtain interatomic force constants in real
space C(R). For polar materials: a term having the same behaviour for q → 0
as the non-analytic term is subtracted from C(qi) before the Fourier Transform
and re-added to C(R), so that no problem related to non-analytic behaviour
and related long-rangeness arises in the Fourier Transform (code q2r.x)

• Calculate phonons at any wave-vector, diagonalizing the dynamical matrix:

αβ 1 X αβ
Dst (q) =√ Cst (R) exp(iq · R)
M s Mt R

using code matdyn.x

Sample input files in examples disp.tar.gz

 Fast algorithm for specific cases

A simplified, faster algorithm exists if i) you sample the Brillouin Zone with only
the Γ point (e.g. molecules, large unit cells), ii) you need phonon modes only at
Γ, and iii) you use only norm-conserving pseudopotentials (no USPP or PAW).

• Perform the scf calculation at equilibrium positions with Γ−point tricks: code
pw.x with input card
K POINTS gamma

• use specialized code phcg.x to find C(q = 0); specify option epsil=.true.
to calculate Z ∗ and ∞.

• Impose Acoustic Sum Rule (ASR), add the nonanalytic LO-TO splitting,
calculate IR cross sections with code dynmat.x

Nonlinear quantities (e.g. Raman) not implemented.