Supporting Information: Polariton assisted incoherent to coherent excitation energy transfer between colloidal quantum dots
I Nanocrystal Configurations
We consider quantum dot (QD) systems. The nm CdSe core with a -monolayer CdS shell QD contains a total of Cd atoms, Se atoms, and S atoms. The nm CdSe core with a -monolayer CdS shell QD contains a total of Cd atoms, Se atoms, and S atoms. The nm CdSe core with a -monolayer CdS shell QD contains a total of Cd atoms, Se atoms, and S atoms.
The Stillinger–Weber force field [zhou2013stillinger] was utilized to determine the equilibrium structure and normal vibrational modes using LAMMPS.[plimpton1995fast] Following minimization, the outermost layer was replaced by ligands with a modification of the pseudopotential to represent the passivation layer.[rabani1999electronic]
II Polaron transformation
The total Hamiltonian in polaritonic basis:
(S1) |
Apply a unitary polaron transformation:[jasrasaria2023circumventing, peng2023polaritonic]
(S2) | ||||
(S3) | ||||
(S4) | ||||
(S5) |
Use the relationship:
(S6) | ||||
(S7) | ||||
(S8) |
Eq. S3 transforms the phonon bath part:
(S9) |
Eq. S4 transforms the diagonal system part, which is unchanged:
(S10) |
Eq. S5 transforms the polariton-phonon interaction part:
(S11) |
Then the transformed total Hamiltonian is given by:
(S12) |
We label reorganization energy and the transformed polariton-phonon coupling , then total Hamiltonian can be written as:
(S13) |
III Time–local Redfield Equations
We use polaritonic basis , to express the reduced density matrix and the system Hamiltonian:
(S14) | |||
(S15) |
Using second order perturbation in , the equation of motion of the reduced density matrix is given by:[nitzan2006chemical]
(S16) |
where
(S17) | ||||
else: | (S18) |
Employing a time local approximation, with ,[nitzan2006chemical] we arrive at:
(S19) |
Here we could see that, the so-called Redfield tensor: depends on time.
IV Calculating
We represent the bath position () and momentum () operators using raising and lowering operators ( and , respectively):
(S20) | ||||
(S21) |
Recall the dressed phonon coupling element, ,
(S22) |
In the above equation, , the coupling matrix element between two polaritonic states and and phonon mode . was obtained by applying the unitary transformation that diagonalizes to , for each mode (see main text). The corresponding correlation function, (Eq. (9)) can then be expressed as :
(S23) |
where
(S24) | ||||
(S25) |
so
(S26) | ||||
(S27) |
where
(S28) | ||||
(S29) |
Using the commutation relationship:
(S30) |
the correlation function can be expressed as
(S31) |
where
(S32) |
(S33) |
(S34) |
and .
Similarly, the average is given by:
(S35) |
V Effective Coupling
V.1 Three level system
We consider a three level system representing a donor, acceptor coupled directly and both are coupled to a bridge state (cavity). The system Hamiltonian is written as:
(S36) |
where the donor and acceptor states with the energies and are directly coupled by . The bridge state couples to the donor and acceptor with coupling strength . The goal is to rewrite the eigenvalue problem
(S37) |
in the donor-acceptor subspace. The three eigenvalues (we assume for clarity that ) are given by:
(S38) | ||||
(S39) | ||||
(S40) |
The corresponding eigenvectors can be obtained from:
(S41) | ||||
(S42) | ||||
(S43) |
Replacing in the last two equations by the solution of the first one, , we find:
(S44) | ||||
(S45) |
which can be rewritten in a similar form to an eigenvalue problem in the Hilbert space of the donor and acceptor:
(S46) |
where
(S47) |
and the effective coupling
(S48) |
depend on For the two eigenvalues and we find:
(S49) |
For small values , and for large values of , . This implies that for large coupling of the donor and acceptor to the bridge results in an effective direct coupling between the donor and acceptor that scales with .