Benchmarking the Bethe-Salpeter Formalism on a Standard Organic Molecular Set

被引:181
作者
Jacquemin, Denis [1 ,2 ]
Duchemin, Ivan [3 ]
Blase, Xavier [4 ,5 ]
机构
[1] Univ Nantes, Lab CEISAM, CNR, UMR 6230, F-44322 Nantes 3, France
[2] Inst Univ France, F-75005 Paris 5, France
[3] Univ Grenoble Alpes, INAC, SP2M L Sim, CEA UJF Cedex 09, F-38054 Grenoble, France
[4] CNRS, Inst NEEL, F-38042 Grenoble, France
[5] Univ Grenoble Alpes, Inst NEEL, F-38042 Grenoble, France
基金
欧洲研究理事会;
关键词
DENSITY-FUNCTIONAL THEORY; ELECTRONICALLY EXCITED-STATES; COUPLED-CLUSTER; TD-DFT; SPECTROSCOPIC PROPERTIES; BIOLOGICAL CHROMOPHORES; EXCITATION-ENERGIES; OPTICAL-ABSORPTION; 0-0; TRANSITIONS; N-H;
D O I
10.1021/acs.jctc.5b00304
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We perform benchmark calculations of the Bethe Salpeter vertical excitation energies for the set of 28 molecules constituting the well-known Thiel's set, complemented by a series of small molecules representative of the dye chemistry field. We show that Bethe Salpeter calculations based on a molecular orbital energy spectrum obtained with non-self-consistent G(0)W(0) calculations starting from semilocal DFT functionals dramatically underestimate the transition energies. Starting from the popular PBEO hybrid functional significantly improves the results even though this leads to an average -0.59 eV redshift compared to reference calculations for Thiel's set. It is shown, however, that a simple self-consistent scheme at the GW level, with an update of the quasiparticle energies, not only leads to a much better agreement with reference values, but also significantly reduces the impact of the starting DFT functional. On average, the Bethe Salpeter scheme based on self-consistent GW calculations comes close to the best timedependent DFT calculations with the PBEO functional with a 0.98 correlation coefficient and a 0.18 (0.25) eV mean absolute deviation compared to TD-PBEO (theoretical best estimates) with a tendency to be red-shifted. We also observe that TD-DFT and the standard adiabatic Bethe Salpeter implementation may differ significantly for states implying a large multiple excitation character.
引用
收藏
页码:3290 / 3304
页数:15
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