Relaxing Constrained Amplitudes: Improved F12 Treatments of Orbital Optimization and Core–Valence Correlation Energies

We present a Lagrangian correction for the energy change upon releasing constraints imposed on coupled cluster amplitudes. We demonstrate that our correction (i) eliminates the systematic basis set error of the posthoc F12 treatment in orbital optimized methods and (ii) can be used to relax the F12...

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Bibliographic Details
Published inJournal of chemical theory and computation Vol. 14; no. 11; pp. 5435 - 5440
Main Authors Tew, David P, Kats, Daniel
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 13.11.2018
Subjects
Amplitudes
Correlation coefficients
Error correction
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Summary:We present a Lagrangian correction for the energy change upon releasing constraints imposed on coupled cluster amplitudes. We demonstrate that our correction (i) eliminates the systematic basis set error of the posthoc F12 treatment in orbital optimized methods and (ii) can be used to relax the F12 amplitudes and significantly reduce the sensitivity of the core–valence correlation energies to the exponent of the correlation factor, while retaining the low cost of the fixed amplitude approach.
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ISSN:1549-9618
1549-9626
DOI:10.1021/acs.jctc.8b00792