Assessing density functional theory in real-time and real-space as a tool for studying bacteriochlorophylls and the light-harvesting complex 2

Schelter, Ingo; Foerster, Johannes M.; Gardiner, Alastair T.; Roszak, A.W.; Cogdell, Richard J.; Ullmann, G. Matthias; Queiroz, Thiago Branquinho de; Kümmel, Stephan

doi:10.1063/1.5116779

Cited by 15 publications

(14 citation statements)

References 130 publications

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“…TD-LDA leads to spurious excitations with charge transfer character in between Q y and Q x , as well as slightly above Q x , depending on the structure, as discussed below and in the literature. 47 TDDFT with the optimally tuned ωPBE results in good agreement with experiment for all three excitations, albeit with slightly higher MAEs of 170, 50, and 250 meV for Q y , Q x , and B, respectively.…”

Section: ■ Results and Discussionsupporting

confidence: 90%

“…TD-LDA's severe underestimation of charge transfer excitations is well known 9 and leads to spurious excitations with charge transfer character at energies between Q y and Q x for BCL a. 47 Our comparison of structures "A" and "R" shows that while the energy of Q y and Q x is changing only slightly when TD-LDA is used, the relative position of these spurious low-oscillator strength excitations depends strongly on the structure. G 0 W 0 @LDA+BSE results in a very different, albeit no more reassuring, picture.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…5,6 The accuracy of its approximations and implementations has been tested for a variety of biochromophores. 7,8,47 However, TDDFT's standard approximations are inadequate for describing long-range charge transfer excitations 9 and highenergy Rydberg states 10 due to self-interaction errors and an incorrect asymptotic behavior. Exchange−correlation (xc) functionals that contain long-range exact exchange, such as optimally tuned range-separated hybrid functionals (OT-RSH), can be employed as a remedy in such cases, 11,12 but the use of such functionals requires a tedious per-system tuning procedure.…”

Section: ■ Introductionmentioning

confidence: 99%

“…In the field of finite organic and biological molecular systems, neutral excitations and optical spectra are predominantly calculated using time-dependent density functional theory (TDDFT). In conjunction with model Hamiltonian approaches, TDDFT has been employed for the simulation of large photosynthetic pigment–protein complexes. , The accuracy of its approximations and implementations has been tested for a variety of biochromophores. ,, However, TDDFT’s standard approximations are inadequate for describing long-range charge transfer excitations and high-energy Rydberg states due to self-interaction errors and an incorrect asymptotic behavior. Exchange–correlation (xc) functionals that contain long-range exact exchange, such as optimally tuned range-separated hybrid functionals (OT-RSH), can be employed as a remedy in such cases, , but the use of such functionals requires a tedious per-system tuning procedure.…”

Section: Introductionmentioning

confidence: 99%

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Assessment of the Ab Initio Bethe–Salpeter Equation Approach for the Low-Lying Excitation Energies of Bacteriochlorophylls and Chlorophylls

Hashemi

Leppert

2021

J. Phys. Chem. A

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Bacteriochlorophyll and chlorophyll molecules are crucial building blocks of the photosynthetic apparatus in bacteria, algae, and plants. Embedded in transmembrane protein complexes, they are responsible for the primary processes of photosynthesis: excitation energy and charge transfer. Here, we use ab initio many-body perturbation theory within the GW approximation and Bethe–Salpeter equation (BSE) approach to calculate the electronic structure and optical excitations of bacteriochlorophylls a , b , c , d , and e and chlorophylls a and b . We systematically study the effects of the structure, basis set size, partial self-consistency in GW , and the underlying exchange–correlation approximation and compare our calculations with results from time-dependent density functional theory, multireference RASPT2, and experimental literature results. We find that optical excitations calculated with GW +BSE are in excellent agreement with experimental data, with an average deviation of less than 100 meV for the first three bright excitations of the entire family of (bacterio)chlorophylls. Contrary to state-of-the-art time-dependent density functional theory (TDDFT) with an optimally tuned range-separated hybrid functional, this accuracy is achieved in a parameter-free approach. Moreover, GW +BSE predicts the energy differences between the low-energy excitations correctly and eliminates spurious charge transfer states that TDDFT with (semi)local approximations is known to produce. Our study provides accurate reference results and highlights the potential of the GW +BSE approach for the simulation of larger pigment complexes.

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Section: ■ Results and Discussionsupporting

confidence: 90%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Assessment of the Ab Initio Bethe–Salpeter Equation Approach for the Low-Lying Excitation Energies of Bacteriochlorophylls and Chlorophylls

Hashemi

Leppert

2021

J. Phys. Chem. A

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“…In conjunction with model Hamiltonian approaches, TDDFT can be employed for the simulation of photosynthetic pigment-protein complexes 3,4 . The accuracy of its approximations and implementations has been tested for a variety of biochromophores [5][6][7] . However, TDDFT's standard approximations are inadequate for describing long-range charge transfer (CT) excitations 8 and highenergy Rydberg states 9 due to their incorrect asymptotic behavior.…”

Section: Introductionmentioning

confidence: 99%

Assessment of the Ab Initio Bethe-Salpeter Equation Approach for the Low-Lying Excitation Energies of Bacteriochlorophylls and Chlorophylls

Hashemi,

Leppert

2020

Preprint

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Bacteriochlorophyll and chlorophyll molecules are crucial building blocks of the photosynthetic apparatus in bacteria, algae and plants. Embedded in transmembrane protein complexes, they are responsible for the primary processes of photosynthesis: excitation energy and charge transfer. Here, we use ab initio many body perturbation theory within the GW approximation and Bethe-Salpeter equation (BSE) approach to calculate the electronic structure and optical excitations of bacteriochlorophylls a, b, c, d and e and chlorophylls a and b. We systematically study the effects of structure, basis set size, partial self-consistency in the GW approach and the underlying exchange-correlation approximation. Furthermore, we compare our calculations with results from time-dependent density functional theory, and calculations and experimental results from the literature, and find that optical excitations calculated with GW +BSE are in very good agreement with experimental data, on average underestimating the Q y and Q x excitations of the entire family of (bacterio)chlorophylls by less than 0.1 eV. Moreover, the GW +BSE approach predicts the energy difference between the two excitations correctly, highlighting the potential of this method for the simulation of larger pigment complexes.

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Notizen aus der Chemie

Heine¹,

Hoch²,

Jahn³

et al. 2019

Nachr Chem

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Assessing density functional theory in real-time and real-space as a tool for studying bacteriochlorophylls and the light-harvesting complex 2

Cited by 15 publications

References 130 publications

Assessment of the Ab Initio Bethe–Salpeter Equation Approach for the Low-Lying Excitation Energies of Bacteriochlorophylls and Chlorophylls

Assessment of the Ab Initio Bethe–Salpeter Equation Approach for the Low-Lying Excitation Energies of Bacteriochlorophylls and Chlorophylls

Assessment of the Ab Initio Bethe-Salpeter Equation Approach for the Low-Lying Excitation Energies of Bacteriochlorophylls and Chlorophylls

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