Wavefunction frozen-density embedding with one-dimensional periodicity: Electronic polarization effects from local...

Area of Science:

• Computational Chemistry
• Materials Science
• Condensed Matter Physics

Background:

• Polarization effects are critical in one-dimensional (1D) systems, particularly in organic semiconductors during charge migration.
• Accurate computation of these effects is challenging due to the infinite nature of 1D systems and the complexity of electron loss/attachment events.

Purpose of the Study:

• To develop an efficient computational approach for treating polarization effects in 1D environments.
• To enable accurate calculations of response to electron loss or attachment in 1D molecular systems.

Main Methods:

• Utilized frozen-density embedding (FDE) to manage polarization in a 1D molecular chain.
• Introduced a novel scheme to compute local perturbations without infinite repetition.
• Employed a first-order equation-of-motion ansatz to efficiently calculate polarization effects, avoiding open-shell calculations.
• Implemented freeze-thaw iterations for wavefunction relaxation in localized subsystems.

Main Results:

• Successfully computed polarization effects in charged tetraazaperopyrenes within 1D chains.
• Demonstrated the efficiency of the proposed FDE-based scheme.
• Avoided the need for infinite system repetition and computationally expensive open-shell calculations.

Conclusions:

• The developed method provides an efficient and accurate way to study polarization in 1D systems.
• The approach is suitable for modeling charge migration phenomena in organic semiconductors.
• The method generates valuable wavefunction-based reference data for electronic couplings in complex 1D environments.