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Updated: Jun 5, 2026
Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Multireference composite approaches for the accurate study of ground and excited electronic states: C2, N2, and O2
1Center for Advanced Scientific Computing and Modeling, Department of Chemistry, University of North Texas, Denton, Texas 76203-5070, USA.
Abstract:
A multireference analog of the correlation consistent composite approach (MR-ccCA) based on complete active space with second-order perturbation theory (CASPT2) has been utilized in an investigation of the ground and valence excited states of C(2), N(2), and O(2). The performance of different second-order multireference perturbation theory methods including second-order n-electron valence state perturbation theory, second-order multireference Møller-Plesset, and second-order generalized van Vleck perturbation theory has been analyzed as potential alternatives to CASPT2 within MR-ccCA. The MR-ccCA-P predicts spectroscopic constants with overall mean absolute deviations from experimental values of 0.0006 Å, 7.0 cm(-1), and 143 cm(-1) for equilibrium bond length (r(e)), harmonic frequency (ω(e)), and term values (T(e)), respectively, which are comparable to the predictions by more computationally costly multireference configuration interaction-based methods.
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