Supplemental material for Enhancement of

the electron-phonon scattering induced by

intrinsic surface plasmon-phonon polaritons

∗,† †,‡ †
David Hagenmüller, Johannes Schachenmayer, Cyriaque Genet, Thomas W.

† †,‡
Ebbesen, and Guido Pupillo

†ISIS (UMR 7006) and icFRC, University of Strasbourg and CNRS, Strasbourg, France

‡IPCMS (UMR 7504), University of Strasbourg and CNRS, Strasbourg, France

E-mail: dhagenmuller@unistra.fr

In this supplemental material (22 pages, 1 gure), we provide details of the calculations

sketched in the main text. The rst section is dedicated to the derivation and diagonalization

of the matter Hamiltonian leading to the hybrid plasmon-phonon modes. In the second

section, we derive the photon and light-matter coupling Hamiltonians, and explain the self-

consistent method used to nd the surface polariton modes of the system. Further details

concerning the theoretical foundations of the model can be found in Ref. [1]. The plasmon,

phonon, and photon admixtures of the polaritons are provided at the end of the section. In

the third section, we derive the coupling Hamiltonian between electronic dark modes and

intramolecular optical phonons, and show in detail how the surface polariton modes can

lead to an enhancement of the electron-phonon scattering in the crystal. In the last section,

we study an elementary plasmonic structure composed of a single metal-dielectric interface,

where phonons in the dielectric region strongly interact with SPPs. We use an eective

model similar to that of Ref. [2], which is based on the SPP quantization scheme detailed

S1
in Refs. [3-5], and show that unphysical behaviors appear in the ultrastrong coupling (USC)

regime.

Diagonalization of the matter Hamiltonian

We rst explain the diagonalization procedure of Hmat in detail. The latter involves both

plasmonic and phononic degrees of freedom through the total polarization eld P = Ppl +Ppn ,
where

1 X 
†

Ppl (R) = dKQ P−K−Q + PKQ e−iQ·R (1)
V K,Q

denotes the plasmon polarization eld and Ppn the phonon polarization. In the case of

†
a 3D free electron gas, the electron-hole excitation operator PKQ = c†K+Q cK is written

in terms of the fermionic operators cK and c†K , which annihilates and creates an electron

with 3D wave vector K, respectively. For long-wavelength excitations with Q  KF , the

†
Hilbert space is restricted to the RPA subspace spanned by the states {|F i , PKQ |F i}, where
c†K |0i is the electron ground state (Fermi sea of the free electron gas), K = |K|
Q
|F i = K<KF

the wave vector modulus, |0i the vacuum state, and KF the Fermi wave vector. In this case,

1 †
it can be shown that PKQ and its hermitian conjugate are bosonic operators satisfying the

†
commutation relation [PKQ , PK 0 Q0 ] = δK,K0 δQ,Q0 . The electronic dipole moment reads

2K + Q
dKQ = −ienK (1 − nK+Q ) ,
(2K + Q) · Q

where nK denotes the Fermi occupation number at zero temperature, namely nK = 1 for

K < KF and nK = 0 for K > KF . The electron eective charge and mass are denoted as

e and m, respectively. Denoting the lattice site positions as Ri , where i ∈ [1, n] with n the

S2
number of unit cell in the crystal, the phonon polarization eld can be written as

s
Z 2N ~ X 
†

Ppn (R) = δ (R − Ri ) Biα + Biα uα . (2)
2M ω0 α,i

Here, uα with α = z,// denotes the polarization (unit) vector of each phonon mode with

the same frequency ω0 , N the number of vibrating ions with eective mass M and charge

†
Z per unit cell, and Biα and Biα respectively annihilates and creates a phonon polarized in

the direction α at the lattice position i. These operators satisfy the bosonic commutation

relation [Biα , Bi†0 α0 ] = δα,α0 δi,i0 . Writing the phonon operators in the Fourier basis: Biα =
√1 BQα e−iQ·Ri ,
P
Q the phonon polarization Eq. (2) takes the form
n

s
Z 2N ~ X  †

−iQ·R
Ppn (R) = B−Qα + BQα uα e , (3)
2M ω0 V a3 Q,α

with a3 the volume of a unit cell. The matter Hamiltonian can be decomposed as Hmat =
P †
Hpl +Hpn +HP2 . The contribution Hpl = K,Q ~∆ξK,Q PKQ PKQ is the eective Hamiltonian

providing the energy ~∆ξK,Q = ~ξK+Q − ~ξK of the electron-hole pairs created across the

Fermi sea. The electron energy (relative to the Fermi energy) is denoted as ~ξK . For

simplicity, we assume a 3D spherical Fermi surface providing ξK = ~(K 2 − KF2 )/(2m). The
P †
free phonon Hamiltonian reads Hpn = Q,α ~ω0 BQα BQα , and the interaction term HP2 is

proportional to the square polarization eld:

Z
1
HP2 = dR P2 (R). (4)
20

This term contains the contributions of both plasmons and phonons ∝ P2pl and ∝ P2pn ,
respectively, as well as a direct plasmon-phonon interaction term ∝ Ppl · Ppn . Replacing

Eqs. (1) and (3) into Eq. (4) and performing the spatial integration, the matter Hamiltonian

S3
is derived as

X X   
† † †
Hmat = ~∆ξK,Q PKQ PKQ + ~ΛQ
KK0 P −K−Q + P KQ P 0
KQ + P −K0 −Q
K,Q K,K0 ,Q
2 
X †
X ~νpn †

†

+ ~ω0 BQα BQα + B−Qα + BQα BQα + B−Qα
Q,α Q,α
4ω0
X   
† †
+ ~µαKQ P−K−Q + PKQ BQα + B−Qα , (5)
K,Q,α

νpn
where we have introduced ΛQ
KK0 =
1
20 ~V
dKQ · dK0 Q and µαKQ = √
20 ~ω0 V
dKQ · uα , with
q
Z2N
νpn = M 0 a3
the ion plasma frequency. The Hamiltonian Eq. (5) can be diagonalized using

6
the Hopeld-Bogoliubov method, by introducing collective eigenmodes in the form

X †
 X †

ΠQj = pKQj PKQ + peKQj P−K−Q + bQαj BQα + bQαj B−Qα .
e (6)
K α

The condition for these modes to diagonalize the Hamiltonian Eq. (5) is then [ΠQj , Hmat ] =
ωj ΠQj .
~e Computing this commutator and introducing the vector

X dKQ X νpn uα  
ZQj = (pKQj − peKQj ) + √ bKQj − ebKQj , (7)
K
20 ~V α
80 ~V ω0

we obtain the transformation coecients entering Eq. (6):

−2dKQ · ZQj −2dKQ · ZQj

pKQj = peKQj =
ej − ∆ξK,Q
ω ω
ej + ∆ξK,Q
r r
20 ~V uα · ZQj 20 ~V uα · ZQj
bQαj = νpn ebQαj = νpn . (8)
ω0 ω ej − ω0 ω0 ω ej + ω0

Introducing the orthogonal basis (Q/Q, uQ1 , uQ2 ), where uQp (p = 1, 2) denote the two

transverse polarization vectors, ZQj can be decomposed into its longitudinal and transverse

components. Solving for the transverse components, one can replace ZQj = ZQj uQp in

S4
Eq. (8), and Eq. (7) turns out to be equivalent to cr (e
ωj )ZQj = 0, where

2 2
ωpl νpn
cr (ω) = 1 − − (9)
ω2 ω 2 − ω02

represents the transverse dielectric function of the crystal. To obtain this result, we have
q
ρe2
used the denition of the electronic plasma frequency ωpl = m0
with ρ the electron density,
P
α uα · uQ,p = 1, as well as the identity

2
1 X 2|dKQ · uQp |2 ∆ξK,Q ωpl
2
∼ , (10)
~0 V K ω 2 − ∆ξK,Q ω2

in the so-called dynamical long-wavelength limit Q  KF , ω  vF Q (vF = ~KF /m is the

Fermi velocity). Note that in this regime, one can use the relation

4e2 nK (1 − nK+Q ) (QK)2 − (K · Q)2

 
2 e2 nK (1 − nK+Q )
|dKQ · uQp | = ∼
Q2 (Q2 + 2K · Q)2 Q2

to put Eq. (10) in the form of the well-known Lindhard function, which describes the longi-

7
tudinal response of a free electron gas. The two eigenvalues ω
ej can be determined by solving

the equation cr (e

ωj ) = 0 , which provides the solutions given by Eq. (1) of the main text.

As detailed in Ref. [1], the vector ZQj can be decomposed as ZQj = Nj Tj uQp when solving

for the transverse modes, where Tj are determined by computing the residues of the inverse

dielectric function

1 X Tj2
=1+ 2−ω 2
,
cr (ω) j=1,2
ω e j

and are derived as

2
ωpl ω22 − ω02 ) + νpn
(e 2
e22
ω 2
ωpl ω12 − ω02 ) + νpn
(e 2
e12
ω
T22 = T12 = . (11)
e22 − ω
ω e12 e12 − ω
ω e22

S5
The constant Nj can be found by using the normalization condition

X
X 
|pKQj |2 − |e
pKQj |2 + |bQαj |2 − |ebQαj |2 = 1,
K α

stemming from the commutation relation [ΠQj , Π†Q0 j 0 ] = δQ,Q0 δj,j 0 . Using Eq. (8) with ZQj =
Nj Tj uQp , as well as the identity

2
1 X 2|dKQ · uQp |2 ∆ξK,Q ωpl
2 ∼ ,
~0 V K ω4
2


ω 2 − ∆ξK,Q

which can be derived similarly as Eq. (10) in the dynamical long-wavelength limit, we obtain

2 2
ωpl νpn
 
1
ej Tj2
= 8~0 V ω + . (12)
Nj2 ej4
ω ωj2 − ω02 )2
(e

Finally, we use Eqs. (1), (3), (6), (8), the decomposition ZQj = Nj Tj uQp , as well as the

identities

X Tj2 X Tj2
=1 = 1,
j
ej2 − ∆ξK,Q
ω 2
j
ej2 − ω02
ω

to write the total (transverse) polarization eld as

X Tj 
†

P(R) = Π−Qjp + ΠQjp e−iQ·R uQp . (13)
Q,j,p
4Nj ω
ej V

Since the crystal is assumed to be isotropic, one can choose the transverse polarization vec-

tors uQp to coincide with uα (α = z,//), and using Eqs. (11) and (12), the polarization eld

Eq. (13) coincides with Eq. (3) of the main text. The matter Hamiltonian in the new basis

ωj Π†Qjα ΠQjα .
P
takes the simple form Hmat = Q,α,j ~e Importantly, the full matter Hamilto-

nian also contains the contribution of the electronic dark modes (electron-hole continuum)

associated to individual electrons. Since the weight of a collective mode ΠQjα on the in-

S6
dividual electronic states goes to zero as the number of electrons goes to innity (which

~ξK c†K cK ,
P
is assumed here), this contribution can be written as K and is included in the

coupling Hamiltonian Hel−pn between the electronic dark modes and phonons derived in the

last section.

Coupling to photons: Surface plasmon-phonon polaritons

In this section, we provide the detailed derivation of the photon Hamiltonian Hpt and the

light-matter coupling term Hmat−pt entering the polariton Hamiltonian Hpol . We then explain

the self-consistent algorithm used to diagonalize Hpol and to nd the surface polariton modes

of the system. The phonon, plasmon, and photon weights of the polaritons are dened at the

end of the section. The displacement and magnetic elds D and H can be found by general-
1
izing Todorov's approach to the case of a double interface, writing them as a superposition
q
40 ~c iq·r
P
of the elds generated by each interfaces m = 1, 2: D(R) = q,m S
e uqm (z)Dqm ,
q
40 ~c iq·r
P
and H(R) = q,m wq S
e vqm (z)Hqm . Here, S denotes the surface of the crystal, and

wq the frequency of the surface polariton modes which are still undetermined at this point.

Denoting by u⊥ the in-plane unit vector perpendicular to both uz and u//, and θ the heaviside
function, the mode functions read

uq1 (z) = −γd θ(−z)eγd z + γcr θ(z)θ(` − z)e−γcr z + γd θ(z − `)e−γcr ` e−γd (z−`) u//
 

+ iq θ(−z)eγd z + θ(z)θ(` − z)e−γcr z + θ(z − `)e−γcr ` e−γd (z−`) uz

 

uq2 (z) = −γd θ(−z)e−γcr ` eγd z − γcr θ(z)θ(` − z)eγcr (z−`) + γd θ(z − `)e−γd (z−`) u//
 

+ iq θ(−z)e−γcr ` eγd z + θ(z)θ(` − z)eγcr (z−`) + θ(z − `)e−γd (z−`) uz ,

 

S7
and

vq1 (z) = θ(−z)eγd z + θ(z)θ(` − z)e−γcr z + θ(z − `)e−γcr ` e−γd (z−`) u⊥

 

vq2 (z) = θ(−z)e−γcr ` eγd z + θ(z)θ(` − z)eγcr (z−`) + θ(z − `)e−γd (z−`) u⊥ .
 

1
dR D2 (R)+ 201c2 dR H2 (R) and performing
R R
Replacing these expressions into Hpt = 20

the integrations, the free photon Hamiltonian is derived as

X  0

mm0
Hpt = ~c Amm
q Dqm D−qm 0 + B
q Hqm H−qm0 , (14)
q,m,m0

with the overlap matrix elements

0 q 2 + γcr
2
q 2 + γd2
Amm 1 − e−2γcr ` + 1 + e−2γcr `


q =
γcr γd
2 
wq 1 − e−2γcr ` 1 + e−2γcr `

0
Bqmm = 2 +
c γcr γd

for m = m0 , and

q 2 + γd2
 
0 −2γcr `
Amm 2 2


q = 2e q − `+ γcr
γd
2
2wq
 
0 1 + γd `
Bqmm = 2 e−2γcr `
c γd

for m 6= m0 . The Hamiltonian Eq. (14) is diagonalized by the transformation Dq± =

√
(Dq2 ± Dq1 ) / 2, where the new eld operators Dqσ and Hqσ satisfy the commutation re-

lations
†
[Dqσ , Dq† 0 σ0 ] = [Hqσ
†
, Hq† 0 σ0 ] = 0, and [Dqσ , Hq† 0 σ0 ] = −iCqσ δq,q0 δσ,σ0 , together with the

† †
properties Dqσ = D−qσ and Hqσ = H−qσ . The constant Cqσ can be determined by using the

Maxwell's equation

d i
D(R) = [Hpt , D(R)] = ∇ × H(R),
dt ~

S8
 wqσ 1
which provides Cqσ = 2cβqσ
. One can then write the eld D(R) in terms of the new photon

eigenmode operators Dq± , and replace it in the light-matter coupling Hamiltonian Hmat−pt =
− 10 dR P(R) · D(R).
R
Together with Eq. (3) of the main text, we obtain

s 
2c X h     i
Hmat−pt = −~ωpl Dq+ iq Π−Qjz + Π†Qjz F+ (Q) + γcr Π−Qj// + Π†Qj// F− (Q)
ω
ej ` Q
h     i
† †
− Dq− iq Π−Qjz + ΠQjz F− (Q) + γcr Π−Qj// + ΠQj// F+ (Q)

(15)

after spatial integration. The function F± (Q) stems from the overlap between the displace-
√
ment and the polarization elds and reads F± (Q) = (F2 (Q) ± F1 (Q)) / 2 with

1 − e−(iqz −γcr )` 1 − e−(iqz +γcr )`

 
−γcr `
F1 (Q) = e F2 (Q) = .
iqz − γcr iqz + γcr

†
fασ (Q)Π†Qjα
P
We now introduce the quasi-2D bright modes πqσj = qz ,α and its hermitian

conjugate, which consist of linear superpositions of the 3D plasmon-phonon hybrid modes.

The function fασ (Q) reads

fz± (Q) = iqNq± F± (Q) f//± (Q) = γcr Nq± F∓ (Q).

The normalization constant Nqσ is determined by imposing the bosonic commutation rela-

[πqσj , πq† 0 σj ] = δq,q0 , 1/N2q± = qz q 2 |F± (qz )|2 + γcr

2
|F∓ (qz )|2 . Trans-
P
tions which provides
P R +∞
forming the summation into an integral qz → `/(2π) −∞ dqz , and using the results

π 1 − e−2γcr `
Z

2
dqz |Fm (Q)| = for m = 1, 2, (16)
γcr

eiqz ` e−iqz `
Z Z
−γcr `
dqz = dqz 2 = 2π`e , (17)
(iqz + γcr )2 (iqz − γcr )

S9
and

eiqz ` e−iqz `
Z Z Z
dqz
dqz = dqz = = 0, (18)
(iqz − γcr )2 (iqz + γcr )2 (iqz ± γcr )2

we nally obtain

` q 2 + γcr
2
 
1 −2γcr `

−γcr ` 2 2


= 1−e + 2`σe q − γcr . (19)
N2qσ 2 γcr

Note that the existence of a symmetry plane at z = `/2 implies that the symmetric and

antisymmetric bright modes commute, i.e. [πqσj , πq† 0 σ0 j 0 ] = δq,q0 δσ,σ0 δj,j 0 , which can be checked
using Eqs. (16), (17), and (18). On the other hand, the commutation relation with respect

to j follows directly from the diagonalization of the matter Hamiltonian presented in the

rst section. One can then use Eq. (19) combined with the denition of the bright modes

to write the light-matter coupling Hamiltonian Eq. (15) in the form given in the main text.

†
fασ (Q)Π†Qjα Γ†qσjs = gασs (Q)Π†Qjα ,
P P
Using the unitary transformation πqσj = qz ,α and qz ,α

with [Γqσjs , Γ†q0 σ0 j 0 s0 ] = δq,q0 δσ,σ0 δj,j 0 δs,s0 , [πqσj , Γ†q0 σ0 j 0 s ] = [πqσj
†
, Γ†q0 σ0 j 0 s ] = 0, and the identities

X
∗
gασs (Q)gασ 0 s0 (Q) = δs,s0 δσ,σ 0

qz ,α
X
∗
fασ (Q)fασ 0 (Q) = δσ,σ 0

qz ,α
X
∗
gασs (Q)fασ 0 (Q) = 0

qz ,α
X X
gασs (Q)gα∗ 0 σs (Q0 ) + fασ (Q)fα∗0 σ (Q0 ) = δα,α0 δQ,Q0 ,
σ,s σ

P †
the matter Hamiltonian can be decomposed as Hmat = q,σ,j ωj πqσj
~e πqσj + Hdark , where
P∞
ωj Γ†qσjs Γqσjs
P
Hdark = q,σ,j s=1 ~e denotes the contribution of the quasi-2D dark modes

which do not interact with light. Leaving this contribution aside, the polariton Hamilto-

nian Hpol of the main text can be diagonalized numerically using a Hopeld-Bogoliubov

S10
 6
transformation. We introduce the polariton eigenmodes of the system in the form

X 
Pqσζ = eqσjζ π †
Oqσjζ πqσj + O −qσj + Xqσζ Dqσ + Yqσζ Hqσ , (20)
j=1,2

which satisfy the eigenvalue equation [Pqσζ , H] = wqσζ Pqσζ . Computing this commutator,

one can show that the polariton frequencies wqσζ in each subspace (q, σ) are given by the 3

positive eigenvalues of the matrix

 
 ω
e1 0 0 0 0 iΩqσ1 Cqσ 
 
 0
 −e
ω1 0 0 0 iΩqσ1 Cqσ  
 
 0 0 ω 0 0 iΩqσ2 Cqσ 
 
e2
Hqσ =


 (21)
 0
 0 0 −e
ω 2 0 iΩ qσ2 C qσ


 
 qσ1 −Ωqσ1 Ωqσ2 −Ωqσ2
Ω 0 2icαqσ Cqσ 
 
0 0 0 0 −2icβqσ Cqσ 0.

Out of these three eigenvalues, only the lowest two correspond to surface modes as located

below the light cone. These two surface modes are denoted as lower and upper polari-

tons with frequencies wqσLP and wqσUP , respectively. In order to compute these frequen-

cies, we use a self-consistent algorithm which consists in starting with a given frequency

wqσLP , then determine the penetration depths in each media from the Helmholtz equation

2
n (wqσLP )wqσLP /c2 = q 2 − γn2 with d = 1 and cr given by Eq. (9), and use the values of γn to

compute the parameters entering the matrix Eq. (21). The latter is diagonalized numerically

allowing to determine the new wqσLP , and the whole process is repeated until convergence

is reached. This method is applied independently for the symmetric and the antisymmetric

modes σ = ±.

S11
The photon, phonon, and plasmon weights of the polaritons modes are directly related to

the transformation coecients entering Eq. (20). From the polariton normalization

X 
eqσjζ |2 − 2iCqσ Xqσζ Y ∗ = 1,
|Oqσjζ |2 − |O qσζ
j=1,2

ζ ∗
the photon weight is dened as Wpt,qσ = −2iCqσ Xqσζ Yqσζ , and we now need to compute

the phonon and plasmon weights of the hybrid plasmon-phonon modes j = 1, 2. This can

be done by realizing that the frequencies ω

e1 and ω
e2 given by Eq. (1) of the main text are

the eigenvalues of the eective plasmon-phonon coupling Hamiltonian Heff = ~ωpl P † P +

ω0 B † B + ~Ω P + P † B + B†



~e , where P and B denote respectively the eective plasmon
p
and phonon bosonic operators, Ω = (νpn /2) ωpl /e
ω0 is the eective coupling strength, and
q
ω
e0 = ω02 + νpn
2 the longitudinal phonon frequency. We introduce the normal modes Pj0 =
Uj P + Uej P † + Vj B + V
ej B † , which satisfy the eigenvalue equation [Pj0 , Heff ] = ω
ej Pj0 . The

coecients Uj , Uej , Vj , and V

ej can then be computed similarly as before by diagonalizing the

associated Hopeld matrix. Using the normalization condition |Uj |2 −|Uej |2 +|Vj |2 −|V
ej |2 = 1,

the phonon and plasmon weights of the polariton ζ are dened as

ζ
X  
Wpl,qσ = |Uj |2 − |Uej |2 |Oqσjζ |2 − |O
eqσjζ |2
j
X  
ζ 2 ej |2 2 2
Wpn,qσ = |Vj | − |V |Oqσjζ | − |Oqσjζ | ,
e
j

P ζ
and satisfy the sum rule i Wi,qσ =1 with i = pt, pl, pn.

Electron-phonon scattering
In this section, we derive the expression of the coupling Hamiltonian Hel−pn between elec-

810
tronic dark modes and intramolecular phonons, and show how the electron-phonon cou-
P e
pling parameter λ is aected by the phonon dressing. The potential V (R) = i V (R − Ri )

S12
generated by the vibrating ions in the crystal is expanded in the vicinity of the equilibrium

positions R0i as Ve (R − Ri ) ≈ Ve (R − R0i ) − ∇Ve (R − R0i ) · Xi . The displacement vector Xi

is proportional to the phonon polarization eld given by Eq. (3), and reads

s
~N a3 X  †

Xi = B−Qα + BQα uα e−iQ·Ri .
2M ω0 V Q,α

− Ri )e−iK·Ri ,
P
Introducing the fermion eld Ψ(R) = K,i cK φ(R where φ(R − Ri ) denotes

a Wannier function localized on site i, the electron-phonon coupling Hamiltonian reads

X Z
Hel−pn = ~ξK c†K cK −e dR Ψ† (R)V (R)Ψ(R),
K

where the bare phonon contribution is contained in the polariton Hamiltonian derived in the

previous section. Using these expressions and retaining only the diagonal terms evaluated

at the same position (intramolecular vibrations), Hel−pn takes the form

X X  
Hel−pn = ~ξK c†K cK + ~Mc†K cK−Q †
BQα + B−Qα , (22)
K K,Q,α

q
NV
with the coupling constant M = eV00 2~M ω0 a3
independent on the wave vector, and
R
V00 = dR |φ(R)|2 ∇Ve (R) · uα . Electron-phonon interactions are often characterised by

the dimensionless coupling parameter λ, which quanties the electron mass renormalization

11,12
due to the coupling to phonons. At zero temperature, λ reads

1 X

λ= δ(ξK )< −∂ω ΣK (ω)|ω=0 , (23)
N3D K

P V mKF
where < stands for real part, N3D = K δ(ξK ) = 2π 2 ~
is the 3D electron density of states at

the Fermi level, and ∂ω ΣK (ω)|ω=0 denotes the frequency derivative of the retarded electron

13
self-energy ΣK (ω) evaluated at ω = 0. An equation of motion analysis of the electron

S13
Green's function (GF) GK (τ ) = −ihcK (τ )c†K (0)i allows to write the electron self-energy as

dω 0
X Z
ΣK (ω) = i|M| 2
GK−Q (ω + ω 0 )BQα (ω 0 ), (24)
Q,α
2π

R
where BQα (ω) = −i dτ eiωτ hBQα (τ )B−Qα (0)i is the phonon GF written in the frequency do-
†
main, and BQα = BQα + B−Qα . In the absence of phonon-photon coupling (νpn = 0), there is
no hybridization between phonons and plasmons, nor is there coupling to photons. Phonons
P †
therefore enter the Hamiltonian Hpol only in the free contribution Hpn = Q,α ~ω0 BQα BQα .
In this case, the equation of motion analysis simply provides BQα (ω) = 2ω0 /(ω 2 − ω02 ). Us-

0
ing this expression together with the non-interacting electron GF GK (ω) = 1/(ω − ξK ) in

12
Eq. (24), the retarded electron self-energy is derived as

 
0 X
2 1 − nK−Q nK−Q
ΣK (ω) = |M| +
+ , (25)
Q,α
ω − ξK−Q − ω0 + i0 ω − ξK−Q + ω0 + i0+

where 0+ denotes a vanishing positive number. As detailed in the chapter 6 of Ref. [12], we

keep only the terms ∝ nK−Q in Eq. (25), and calculate the quantity ∂ω ΣK (ω)|ω=0 . We then
R K−Q ∂n
use an integration by parts and consider only the term ∝ dQ ∂ξK−Q . We nally obtain the

electron-phonon coupling parameter Eqs. (23) for νpn = 0:

2|M|2 X X 2|M|2 N3D

λ0 = δ(ξK ) δ(ξK−Q ) = .
N3D ω0 K Q
ω0

In the presence of phonon-photon coupling (νpn 6= 0), the phonon dynamics is governed by the
Hamiltonian Hpol , which includes the coupling of phonons to plasmons and photons. Using

Eqs. (6), (8), (11), and (12) of the rst section, we express the 3D phonon operators BQα
†
and BQα in terms of the 3D hybrid modes ΠQαj and Π†Qαj , and then project the latter onto

the quasi-2D bright and dark modes dened in the previous section such that the electron-

~ξK c†K cK + Hel−pn + Hel−pn .

P (B) (D)
phonon Hamiltonian Eq. (22) takes the form Hel−pn = K The

S14
contribution of the bright modes reads

XX  
(B)
Hel−pn = ∗
~Mηj fασ (Q)c†K cK−Q πqσj + π−qσj
†
,
K,Q α,σ,j

q
ω0 /eωj νpn ωpl
where ηj = χj ωj )4 +χ2j
(ωpl /e
(χj = ej2 −ω02
ω
) is associated to the hybrid modes weights of the

phonons. Similarly, the contribution of the dark modes is

X X  
(D)
Hel−pn = ∗
~Mηj gασs (Q)c†K cK−Q Γqσjs + Γ†−qσjs .
K,Q α,σ,j,s

(B) (D)
Using the Hamiltonians Hel−pn and Hel−pn , the electron self-energies due to the interaction

with bright and dark modes are derived as

dω 0
X Z
(B)
ΣK (ω) = iηj2 |Mfασ (Q)|2GK−Q (ω + ω 0 )Pqσj (ω 0 ) (26)
Q,α,σ,j
2π
dω 0
X Z
(D)
ΣK (ω) = iηj2 |Mgασs (Q)|2 GK−Q (ω + ω 0 )Gqσjs (ω 0 ). (27)
Q,α,σ,j,s
2π

Here, Pqσj (ω) and Gqσjs (ω) denote the bright and dark mode GFs, respectively, dened
R R
as Pqσj (ω) = −i dτ eiωτ hΥqσj (τ )Υ−qσj (0)i and Gqσjs (ω) = −i dτ eiωτ hΞqσjs (τ )Ξ−qσjs (0)i,
†
with Υqσj = πqσj +π−qσj and Ξqσjs = Γqσjs +Γ†−qσjs . We now decompose the electron-phonon

coupling parameter into its bright and dark mode contributions, which are respectively

associated to the self-energies Eqs. (26) and (27): λ = λ(B) + λ(D) for νpn 6= 0, and λ0 =
(B) (D)
λ0 + λ0 in the case νpn = 0. For νpn = 0, the bright and dark mode GFs read Pqσj (ω) =
ωj /(ω 2 − ω
Gqσjs (ω) = 2e ej2 ), with ω
e 1 = ω0 , ω
e2 = ωpl , η1 = 1, and η2 = 0 . Using these GFs

0
together with GK (ω) = 1/(ω − ξK ) in Eqs. (26) and (27), we proceed as before and nd

(B) 2|M|2 X X
λ0 = δ(ξK ) |fασ (Q)|2 δ(ξK−Q ) (28)
N3D ω0 K Q,α,σ

(D) 2|M|2 X X
λ0 = δ(ξK ) |gασs (Q)|2 δ(ξK−Q ). (29)
N3D ω0 K Q,α,σ,s

S15
For νpn 6= 0, the dark modes become hybrid plasmon-phonon modes, but do not interact

with photons. Still using the same procedure with the GF ωj /(ω 2 − ω
Gqσjs (ω) = 2e ej2 ) in

0
Eq. (27) and GK (ω) = 1/(ω − ξK ), we obtain

2|M|2 X ηj2 X X
λ(D) = δ(ξK ) |gασs (Q)|2 δ(ξK−Q ). (30)
N3D j ωej K Q,α,σ,s

ηj2 1 (D)
λ(D) = λ0
P
Interestingly, the sum rule j ω
ej
= ω0
implies that , which means that the

hybridization between plasmons and phonons can not solely lead to a modication of the

electron-phonon scattering at the level of the RPA.

13,14
We now use the equation of motion theory to calculate the bright mode GF Pqσj (ω)
for νpn 6= 0: We start from the Heisenberg equation of motion

∂ 2 Υqσj (τ )
= −[Hpol , [Hpol , Υqσj ]](τ ),
∂τ 2

P
and calculate the double commutator. A vanishing source term q,σ,j Jqσj Υ−qσj is then

added to Hpol , and we calculate the functional derivative of the obtained equation of motion
with respect to Jqσj (0). The bright mode GF can be written as

R
hΥqσj (τ )Υ−qσj (0)e−i dτ1 Hpol (τ1 ) i0 δhΥqσj (τ )i
Pqσj (τ ) = −i −i
R
dτ H (τ )
= ,
he 1 pol 1 i0 δJqσj (0)

where h· · · i0 denotes the expectation value in the non-interacting ground state of Hpol (with-

δhDqσ (τ )i
out the light-matter coupling term Hmat−pt ). Introducing the photon GF Dqσ (τ ) = δJqσj (0)
,

we obtain the following set of equations in the frequency domain:

s
Cqσ βqσ 0 X
Dqσ (ω) = Dqσ (ω) Ωqσj Pqσj (ω)
2 αqσ j

Pqσj (ω) = P0qσj (ω) + Ωqσj P0qσj (ω)Dqσ (ω),

S16
 2Wqσ
where D0qσ (ω) = ω 2 −Wqσ
2 and P0qσj (ω) = 2e
ωj /(ω 2 − ω
ej2 ) denote the non-interacting photon
p
and bright mode GFs, and Wqσ = 2cCqσ αqσ βqσ plays the role of the photon frequency.
Solving for Pqσj (ω), we obtain

j0j0 0 jj 0


P0qσj 1 − Sqσ Pqσj 0 + P0qσj P0qσj 0 Sqσ
Pqσj (ω) =
   0 2 j 0 6= j, (31)
jj 0 j0j0 0 jj
1 − Sqσ Pqσj 1 − Sqσ Pqσj 0 − P0qσj P0qσj 0 Sqσ

2 β Ω
2cCqσ
jj 0 qσ qσj Ωqσj 0
with the photon self-energy Sqσ (ω) = . Note that the polariton frequencies
(ω2 −Wqσ
2
)
wqσζ correspond to the poles of Pqσj (ω), and can be determined by solving the associated

sixth-order polynomial equation. Proceeding as before, we use the GF Eq. (31) together

0
with GK (ω) = 1/(ω − ξK ) in Eq. (26), as well as Eqs. (29) and (30), and obtain the relative

enhancement of the electron-phonon coupling parameter:

∆λ λ − λ0 1 X X
≡ = 2 δ(ξK ) (ϕqσ − 1) |fασ (Q)|2 δ(ξK−Q ),
λ0 λ0 N3D K Q,α,σ

where the function ϕqσζ describes the renormalization of the phonon energy due to the

coupling to plasmons and photons, and depends on the polariton frequencies as

2



XX wqσζ ej20
−ω 2
wqσζ 2
− Wqσ 2
+ 4cCqσ ej 0 Ωqσj 0 (Ωqσj − Ωqσj 0 )
βqσ ω
ϕqσ = ηj2 ω
ej ω0 (1 − δj,j 0 ) 2
Q 2 2

.
ζ j,j 0
wqσζ ζ 0 6=ζ wqσζ − wqσζ 0

One can then transform the summation over Q into an integral, and write the relative

∆λ
R1
enhancement in the simple form
λ0
= 0
dx xF (x), where x = Q/(2KF ), and F (x) is a
q , qez ) = σ,α (ϕqσ − 1) |fασ (Q)|2 with the replacements
P
dimensionless function dened as F (e
√
qe = q/(2KF ) → x 1 − x2 and qez = qz /(2KF ) → x2 .

S17
Eective quantum model in the USC regime
In this section, we show that an eective quantum model similar to that of Ref. [2] exhibits

unphysical behaviors in the ultrastrong coupling regime. We consider a single metal-dielectric

interface featuring a plasmon mode with plasma frequency ωm in the metal region, and a

collection of vibrating ions with frequency ω0 forming a lattice embedded in the dielectric

region of permittivity 1 (e.g. air). Phonons are polarized in the directions uz and u//,
and both the metal and dielectric regions extend to innity on each side. In the eective

quantum model of Ref. [ 2], the Power-Zienau-Woolley Hamiltonian of the system reads

Hpol = Hspp +Hpn−spp +Hpn +HP2 , where Hspp is the eective SPP Hamiltonian, Hpn−spp is the
P †
SPP-phonon coupling, and Hpn = Q,α ~ω0 BQα BQα is the phonon Hamiltonian given in the
1
R
rst section. The term proportional to the square polarization reads HP2 =
20
dR P2pn (R),
where the phonon polarization eld Ppn is given by Eq. (3). As a particular case of the

results presented in the rst section, one can show that the overall phonon contribution to

the Hamiltonian can be put in the diagonal form Hpn + HP2 = ~e

ω0
P e† B
BQα Qα , with the
e
Q,α

transformation

ω
e 0 + ω0 e ωe0 − ω0 e † † e0 − ω0 e
ω ωe0 + ω0 e †
BQ,α = √ BQ,α − √ B B−Q,α =− √ BQ,α + √ B . (32)
2 ω0 ω e0 2 ω0 ωe0 −Q,α 2 ω0 ω
e0 2 ω0 ωe0 −Q,α
q
The longitudinal phonon frequency is dened as e0 = ω02 + νpn
ω 2 with νpn the ion plasma

frequency. The eective SPP Hamiltonian reads

Z Z
1 2 1
Hspp = dR D (R) + dR H2 (R).
20 20 c2

In contrast to the model presented in the previous sections, here, the displacement and

magnetic elds D and H contain the contribution of the plasmon polarization and do not

S18
involve pure photonic degrees of freedom. The displacement eld can be written as

s
X 0 ~wq0
D(R) = i 0
(aq − a†−q )Uq eiq·r , (33)
q
2SLeff (wq )

with S an arbitrary (large) surface in the plane, and aq and a†q the annihilation and creation

operators of a SPP with frequency wq0 , which satisfy the bosonic commutation relations

[aq , a†q0 ] = δq,q0 . The mode functions read

 
q
Uq = u// − uz e−γd z ,
γd

and the penetration depths in the metal and dielectric regions γm and γd are related to
q
2
the SPP frequency via the Helmholtz equation γm = q 2 − m (ξq ) wq0 /c2 and γd =
q
2
q 2 − wq0 /c2 . The SPP frequency wq0 is solution of the equation

s
m (ω) + 1
ω = qc ,
m (ω)

with m (ω) = 1 − (ωm /ω)2 the Drude permittivity of the (lossless) metal. According to the

SPP quantization scheme detailed in Ref. [ 5], the eective quantization length Leff (ω) is

dened as

" #
2 2 2
q2 1 ω2
   
1 q d [ωm (ω)] m (ω) ω 1
2Leff (ω) = 1+ 2 + + 1+ 2 + .
2γm γm dω γm c2 2γd γd |γd |2 c2

35
With these denitions, one can show that the eective SPP Hamiltonian takes the usual

wq0 a†q aq .
P
form Hspp = q Expressing the phonon polarization eld Eq. (3) in terms of the

new operators B e†
eQ,α and B
−Q,α dened by Eq. (32), and using the displacement eld Eq. (33),

S19
 Hph−spp = − 10 dR Ppn (R) · D(R)
R
the phonon-SPP coupling Hamiltonian takes the form

X
 
Hph−spp = i~Ωq b−q + b†q aq − a†−q ,
q

with the vacuum Rabi frequency

s s
wq0 q2
Ωq = νpn 1+ .
ω0 Leff (wq0 )γd
8e γd2

Similarly as in the second section, the quasi-2D phonon operators are dened as bq =
P eQ,z −B
(q/γd )B eQ,//
Nq qz γd −iqz
, where the normalization Nq is determined by the bosonic commu-

1+(q/γd )2
[bq , b†q ] = 1, 1
P
tation relation which provides
N2q
= qz γd2 +qz2
. Gathering the dierent

contributions, the polariton Hamiltonian reads

X X
  X
Hpol = ~wq0 a†q aq + i~Ωq b−q + b†q aq − a†−q + ~e
ω0 b†q bq ,
q q q

and can be diagonalized using a Hopeld-Bogoliubov transformation. The two resulting

polaritons modes are represented on Fig. S1 for νpn = 0.01ω0 (dotted lines), νpn = 0.5ω0
(dashed lines), and νpn = ω0 (solid lines). The lower ζ = LP and upper ζ = UP polaritons

with frequency wqζ are depicted as red and blue lines, respectively. While the limiting
√
behaviors of the LP wqLP ∼ qc for q → 0 and the UP wqUP → ωm / 2 for q → ∞ are

properly described by the model, wqUP for q →0 and wqLP for q →∞ feature unphysical

behaviors in the ultrastrong coupling regime, i.e. when νpn is a non-negligible fraction of

ω0 . Indeed, wqLP exhibits irregularities in the regime of large detunings q  q0 (see inset),

and becomes larger than ω0 while increasing the coupling strength νpn . We conclude that

the eective quantum model based on quantized SPPs is well suited as long as the coupling

strength does not exceed a few percent of the associated transition frequency, and therefore

fails in the ultrastrong coupling regime.

S20
 102
1.3
1.2
1.1
101 1
2 10 100

100

10-1
10-1 100 101 102

Figure S1: Log-log scale: Normalized polariton frequencies wqζ /ω0 versus in-plane wave
vector q/q0 (q0 = ω0 /c), for νpn = 0.01ω0 (dotted lines), νpn = 0.5ω0 (dashed lines), and
νpn = ω0 (solid lines). The lower ζ = LP and upper ζ = UP polaritons are depicted as red
and blue lines. The region delimited by the rectangle is magnied in the inset. The plasma
frequency is chosen as ωm = 45ω0 , which corresponds to ~ωm = 9eV (gold or silver) for
~ω0 = 200meV (mid-infrared optical phonons).

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