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Updated: Jul 7, 2025

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Analytical evaluations of the path integral Monte Carlo thermodynamic and Hamiltonian energies for the harmonic
1Department of Physics and Astronomy, Texas A&M University, College Station, Texas 77843, USA.
Abstract:
By using the recently derived universal discrete imaginary-time propagator of the harmonic oscillator, both thermodynamic and Hamiltonian energies can be given analytically and evaluated numerically at each imaginary time step for any short-time propagator. This work shows that, using only currently known short-time propagators, the Hamiltonian energy can be optimized to the twelfth-order, converging to the ground state energy of the harmonic oscillator in as few as three beads. This study makes it absolutely clear that the widely used second-order primitive approximation propagator, when used in computing thermodynamic energy, converges extremely slowly with an increasing number of beads.
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