TY - JOUR

T1 - Benchmarking doubles-corrected random-phase approximation methods for frequency dependent polarizabilities: aromatic molecules calculated at the RPA, HRPA, RPA(D), HRPA(D) and SOPPA levels

AU - Jørgensen, Maria West

AU - Sauer, Stephan P. A.

PY - 2020/6/15

Y1 - 2020/6/15

N2 - The performance of different polarization propagator methods, RPA, RPA(D), HRPA, HRPA(D) and SOPPA have been tested against CC3 values for both static and dynamic polarizabilities. The test set consists of 14 (hetero-)aromatic medium size organic molecules, mostly with a high degree of symmetry. The benchmark of the methods remarkably reveals that RPA and HRPA(D) yield results comparable with the CC3 values and that they outperform SOPPA for these molecules. For a subset of the molecules a comparison could be made to experimental values. The comparison for static polarizabilities proves that RPA and HRPA(D) as well as RPA(D) reproduce experimental values to a satisfying precision, whereas the SOPPA method compared to these two methods appears to perform only adequately. An investigation of the performance of Sadlej’s polarized triple zeta basis set against Dunning’s augcc-pVTZ basis set was also carried out. It is found, that in contrast to other methods, Sadlej’s basis set did not perform sufficiently compared to the larger aug-cc-pVTZ basis set for the RPA based methods.

AB - The performance of different polarization propagator methods, RPA, RPA(D), HRPA, HRPA(D) and SOPPA have been tested against CC3 values for both static and dynamic polarizabilities. The test set consists of 14 (hetero-)aromatic medium size organic molecules, mostly with a high degree of symmetry. The benchmark of the methods remarkably reveals that RPA and HRPA(D) yield results comparable with the CC3 values and that they outperform SOPPA for these molecules. For a subset of the molecules a comparison could be made to experimental values. The comparison for static polarizabilities proves that RPA and HRPA(D) as well as RPA(D) reproduce experimental values to a satisfying precision, whereas the SOPPA method compared to these two methods appears to perform only adequately. An investigation of the performance of Sadlej’s polarized triple zeta basis set against Dunning’s augcc-pVTZ basis set was also carried out. It is found, that in contrast to other methods, Sadlej’s basis set did not perform sufficiently compared to the larger aug-cc-pVTZ basis set for the RPA based methods.

KW - Faculty of Science

KW - polarizability

KW - SOPPA

KW - RPA

KW - RPA(D)

KW - HRPA(D)

KW - quantum chemistry

KW - Ab initio

KW - Aromatic compounds

U2 - 10.1063/5.0011195

DO - 10.1063/5.0011195

M3 - Journal article

C2 - 32571042

VL - 152

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

SN - 0021-9606

M1 - 234101

ER -