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Title: An assessment of low-lying excitation energies and triplet instabilities of organic molecules with an ab initio Bethe-Salpeter equation approach and the Tamm-Dancoff approximation

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4983126· OSTI ID:1543834
 [1];  [1];  [2];  [3]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Univ. Paris-Saclay, Gif-sur-Yvette (France)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Kavli Energy Nanosciences Inst. at Berkeley, Berkeley, CA (United States)
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The accurate prediction of singlet and triplet excitation energies is an area of intense research of significant fundamental interest and critical for many applications. Most calculations of singlet and triplet energies use time-dependent density functional theory (TDDFT) in conjunction with an approximate exchange-correlation functional. In this work, we examine and critically assess an alternative method for predicting low-lying neutral excitations with similar computational cost, the ab initio Bethe-Salpeter equation (BSE) approach, and compare results against high-accuracy wavefunction-based methods. We consider singlet and triplet excitations of 27 prototypical organic molecules, including members of Thiel’s set, the acene series, and several aromatic hydrocarbons exhibiting charge-transfer-like excitations. Analogous to its impact in TDDFT, we find that the Tamm-Dancoff approximation (TDA) overcomes triplet instabilities in the BSE approach, improving both triplet and singlet energetics relative to higher level theories. Lastly, we find that BSE-TDA calculations built on effective DFT starting points, such as those utilizing optimally tuned range-separated hybrid functionals, can yield accurate singlet and triplet excitation energies for gas-phase organic molecules.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1543834
Alternate ID(s):
OSTI ID: 1361875
Journal Information:
Journal of Chemical Physics, Vol. 146, Issue 19; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 68 works
Citation information provided by
Web of Science

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Cited By (14)

The Bethe–Salpeter equation in chemistry: relations with TD-DFT, applications and challenges journal January 2018
The Bethe–Salpeter formalism with polarisable continuum embedding: reconciling linear-response and state-specific features journal January 2018
Ab initio modelling of local interfaces in doped organic semiconductors journal January 2020
Implicit and explicit host effects on excitons in pentacene derivatives journal March 2018
On the possibility of singlet fission in crystalline quaterrylene journal May 2018
Communication: A hybrid Bethe–Salpeter/time-dependent density-functional-theory approach for excitation energies journal September 2018
Ionized, electron-attached, and excited states of molecular systems with spin–orbit coupling: Two-component GW and Bethe–Salpeter implementations journal May 2019
All-electron ab initio Bethe-Salpeter equation approach to neutral excitations in molecules with numeric atom-centered orbitals journal January 2020
Many-body perturbation theory for understanding optical excitations in organic molecules and solids journal March 2018
Screening mixing GW/Bethe–Salpeter approach for triplet states of organic molecules journal September 2018
Bethe–Salpeter equation for absorption and scattering spectroscopy: implementation in the exciting code journal August 2019
On the Possibility of Singlet Fission in Crystalline Quaterrylene text January 2017
Benchmarks for Electronically Excited States with CASSCF Methods journal May 2019
Electronic Excitations in Complex Molecular Environments: Many-Body Green's Functions Theory in VOTCA-XTP text January 2018

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74 ATOMIC AND MOLECULAR PHYSICS
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