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Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
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Localized optimized orbitals, coupled cluster theory, and chiroptical response properties.

Harley R McAlexander1, Taylor J Mach, T Daniel Crawford

  • 1Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061, USA.

Physical Chemistry Chemical Physics : PCCP
|May 1, 2012
PubMed
Summary

Orbital localization improves the efficiency and accuracy of coupled cluster models for predicting chiroptical properties like optical rotation. This localized approach enables the study of larger molecules than previously possible.

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Area of Science:

  • Computational chemistry
  • Quantum chemistry
  • Theoretical chemistry

Background:

  • Coupled cluster (CC) models are accurate but computationally expensive.
  • Predicting chiroptical properties, such as optical rotation, is crucial in stereochemistry.
  • Orbital localization can potentially reduce the computational cost of CC methods.

Purpose of the Study:

  • To investigate the impact of orbital localization on the accuracy and efficiency of the optimized-orbital coupled cluster (OOCC) model.
  • To assess the performance of a localized correlation scheme for predicting chiroptical properties, specifically optical rotation.
  • To determine the feasibility of applying this method to larger molecular systems.

Main Methods:

  • Computed specific rotations for test cases including (P)-[4]triangulane, (S)-1-phenylethanol, and chiral conformers of fluorinated alkanes.
  • Enforced orbital localization throughout the orbital optimization and linear response (LR) calculations within the OOCC framework.
  • Developed and applied a robust local-correlation scheme.

Main Results:

  • The localized OOCC approach demonstrated accuracy in predicting optical rotation for the tested molecules.
  • The crossover point for localization benefits in OOCC for chiroptical properties occurs at larger molecules compared to ground-state energy calculations.
  • The presented scheme shows reduced computational scaling.

Conclusions:

  • Orbital localization offers a viable strategy to enhance the efficiency of coupled cluster methods for chiroptical property prediction.
  • This localized correlation scheme is suitable for future production-level implementations.
  • The method facilitates the investigation of larger chiral molecules than currently accessible with canonical methods.