TY - JOUR
T1 - Comparing semiclassical mean-field and 1-exciton approximations in evaluating optical response under strong light-matter coupling conditions
AU - Cui, Bingyu
AU - Sukharev, Maxim
AU - Nitzan, Abraham
N1 - Publisher Copyright:
© 2023 Author(s).
PY - 2023/4/28
Y1 - 2023/4/28
N2 - The rigorous quantum mechanical description of the collective interaction of many molecules with the radiation field is usually considered numerically intractable, and approximation schemes must be employed. Standard spectroscopy usually contains some levels of perturbation theory, but under strong coupling conditions, other approximations are used. A common approximation is the 1-exciton model in which processes involving weak excitations are described using a basis comprising the ground state and singly excited states of the molecule cavity-mode system. In another frequently used approximation in numerical investigations, the electromagnetic field is described classically, and the quantum molecular subsystem is treated in the mean-field Hartree approximation with its wavefunction assumed to be a product of single molecules’ wavefunctions. The former disregards states that take long time to populate and is, therefore, essentially a short time approximation. The latter is not limited in this way, but by its nature, disregards some intermolecular and molecule-field correlations. In this work, we directly compare results obtained from these approximations when applied to several prototype problems involving the optical response of molecules-in-optical cavities systems. In particular, we show that our recent model investigation [J. Chem. Phys. 157, 114108 (2022)] of the interplay between the electronic strong coupling and molecular nuclear dynamics using the truncated 1-exciton approximation agrees very well with the semiclassical mean-field calculation.
AB - The rigorous quantum mechanical description of the collective interaction of many molecules with the radiation field is usually considered numerically intractable, and approximation schemes must be employed. Standard spectroscopy usually contains some levels of perturbation theory, but under strong coupling conditions, other approximations are used. A common approximation is the 1-exciton model in which processes involving weak excitations are described using a basis comprising the ground state and singly excited states of the molecule cavity-mode system. In another frequently used approximation in numerical investigations, the electromagnetic field is described classically, and the quantum molecular subsystem is treated in the mean-field Hartree approximation with its wavefunction assumed to be a product of single molecules’ wavefunctions. The former disregards states that take long time to populate and is, therefore, essentially a short time approximation. The latter is not limited in this way, but by its nature, disregards some intermolecular and molecule-field correlations. In this work, we directly compare results obtained from these approximations when applied to several prototype problems involving the optical response of molecules-in-optical cavities systems. In particular, we show that our recent model investigation [J. Chem. Phys. 157, 114108 (2022)] of the interplay between the electronic strong coupling and molecular nuclear dynamics using the truncated 1-exciton approximation agrees very well with the semiclassical mean-field calculation.
UR - http://www.scopus.com/inward/record.url?scp=85153925840&partnerID=8YFLogxK
U2 - 10.1063/5.0146984
DO - 10.1063/5.0146984
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C2 - 37102452
AN - SCOPUS:85153925840
SN - 0021-9606
VL - 158
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 16
M1 - 164113
ER -