2025/12/10 by Martin Chandler, Martin, Chandler, Nicole Spanedda +8
Materials Science · Physics and Astronomy · #Atomic and Molecular Clusters (physics.atm-clus) #Chemical Physics (physics.chem-ph) #Computational Physics (physics.comp-ph) #FOS: Physical sciences #Mesoscale and Nanoscale Physics (cond-mat.mes-hall) #Quantum Dots Synthesis And Properties #Semiconductor Quantum Structures and Devices #Spectroscopy and Quantum Chemical Studies
paper · pdf · doi:10.48550/arxiv.2512.09811
openalex publication_date 2025/12/10 · openalex created_date 2025/12/12 · openalex updated_date 2026/08/01
Accurate prediction of the frequency response of quantum dots under electromagnetic radiation is essential for investigating absorption spectra, excitonic effects, and nonlinear optical behavior in quantum dots and semiconductor nanoparticles. The polarization propagator provides a rigorous framework for evaluating these properties, but its construction is computationally demanding. Challenges arise from the level of electron correlation, the size of the excitonic basis, and the cost of evaluating two-electron integrals. This work addresses these difficulties by developing first- and second-order frequency-dependent polarization propagator calculations for PbS and CdS quantum dots. The propagator is formulated using the electron propagator approach and expressed as the resolvent of the Hamiltonian superoperator. Light-matter interaction is treated using the dipole approximation and represented in a particle-hole excitation operator basis. The correlated ground state is treated at the MP2 level, and all response-matrix terms up to second order in the fluctuating potential are included. A frequency-dependent inverse Krylov subspace method is derived and combined with the folded-spectrum technique to isolate excitation energies within a chosen frequency window. This strategy avoids full diagonalization of the response matrix and significantly reduces computational cost for large systems. The method is implemented in a matrix-free manner in which no explicit response matrix is assembled, and all operations rely on matrix-vector products. UV-VIS excitation spectra of PbS and CdS quantum dots were computed, demonstrating that the inverse Krylov subspace projection approach provides an efficient and accurate approximation for excitation spectra when full diagonalization is computationally prohibitive.