Benchmarking correlated methods for frequency dependent polarizabilities: aromatic molecules with the CC3, CCSD, CC2, SOPPA, SOPPA(CC2) and SOPPA(CCSD) methods

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A benchmark study of several correlated second-order methods for frequency dependent polarizabilities has been carried out. For the benchmark, a set of 14 (hetero-)aromatic medium sized molecules has been chosen. For the first time CC3 polarizabilities are reported for these molecules using Sadlej's polarized triple-zeta basis set and for a subset of these molecules the polarizabilities were obtained at the CC3 level also with the larger aug-cc-pVTZ basis set. These CC3 values are used as the reference values for benchmarking the second-order methods: SOPPA, SOPPA(CC2), SOPPA(CCSD), CC2 as well as CCSD. The influence of different basis sets: aug-cc-pVDZ, aug-cc-pVTZ, aug-cc-pVQZ, d-aug-cc-pVTZ and Sadlej's polarized triple-zeta basis set, on static and frequency dependent polarizabilities was investigated for the full set of molecules at the SOPPA level. It was found, that the choice of basis set had a somewhat greater influence on the frequency dependent polarizabilities than on the static ones, but all effects were small. The aug-cc-pVTZ basis set performed adequately for both static and frequency dependent polarizabilities, having an insignificant offset from the values obtained with the larger d-aug-cc-pVTZ and aug-cc-pVQZ basis sets. Comparing the second-order methods, SOPPA, SOPPA(CC2), SOPPA(CCSD), CC2 as well as CCSD to the CC3 reference values, it was found that the best performing method was CCSD, as expected. The SOPPA method, on the other hand, outperformed the CC2 method, suggesting the use of SOPPA rather than CC2 for polarizabilities, at least for these kinds of molecules. The SOPPA results were found to improve further, when the Møller-Plesset correlation coefficients in the wavefunction were replaced by coupled cluster amplitudes in the SOPPA(CC2) and SOPPA(CCSD) methods. Finally, a comparison was made for a small subset of the molecules between experimental data and calculated polarizabilities. It shows that, for this set of molecules, the trend in the performance of the different second-order methods does not depend on whether the reference values are calculated CC3 values or experimental values.
TidsskriftJournal of Chemical Theory and Computation
Udgave nummer5
Sider (fra-til)3006-3018
Antal sider13
StatusUdgivet - 17 apr. 2020

ID: 239701321