Non-iterative doubles corrections to the random phase and higher random phase approximations: singlet and triplet excitation energies

TY - JOUR

T1 - Non-iterative doubles corrections to the random phase and higher random phase approximations

T2 - singlet and triplet excitation energies

AU - Haase, Pi Ariane Bresling

AU - Faber, Rasmus

AU - Provasi, Patricio F.

AU - Sauer, Stephan P. A.

PY - 2020/1/5

Y1 - 2020/1/5

N2 - The second-order noniterative doubles-corrected random phase approximation (RPA) method has been extended to triplet excitation energies and the doubles-corrected higher RPA method as well as a shifted version for calculating singlet and triplet excitation energies are presented here for the first time. A benchmark set consisting of 20 molecules with a total of 117 singlet and 71 triplet excited states has been used to test the performance of the new methods by comparison with previous results obtained with the second-order polarization propagator approximation (SOPPA) and the third order approximate coupled cluster singles, doubles and triples model CC3. In general, the second-order doubles corrections to RPA and HRPA significantly reduce both the mean deviation as well as the standard deviation of the errors compared to the CC3 results. The accuracy of the new methods approaches the accuracy of the SOPPA method while using only 10–60% of the calculation time.

AB - The second-order noniterative doubles-corrected random phase approximation (RPA) method has been extended to triplet excitation energies and the doubles-corrected higher RPA method as well as a shifted version for calculating singlet and triplet excitation energies are presented here for the first time. A benchmark set consisting of 20 molecules with a total of 117 singlet and 71 triplet excited states has been used to test the performance of the new methods by comparison with previous results obtained with the second-order polarization propagator approximation (SOPPA) and the third order approximate coupled cluster singles, doubles and triples model CC3. In general, the second-order doubles corrections to RPA and HRPA significantly reduce both the mean deviation as well as the standard deviation of the errors compared to the CC3 results. The accuracy of the new methods approaches the accuracy of the SOPPA method while using only 10–60% of the calculation time.

KW - Faculty of Science

KW - RPA(D)

KW - HRPA(D)

KW - Excitation Energy

KW - SOPPA

KW - Quantum Chemistry

KW - Computational Chemistry

U2 - 10.1002/jcc.26074

DO - 10.1002/jcc.26074

M3 - Journal article

C2 - 31576598

SN - 0192-8651

VL - 41

SP - 43

EP - 55

JO - Journal of Computational Chemistry

JF - Journal of Computational Chemistry

IS - 1

ER -