Ground state structures and electronic excitations of biological chromophores at Quantum Monte Carlo/Many Body Green’s Function Theory level

Varsano, Daniele; Coccia, Emanuele; Pulci, Olivia; Conte, Adriano Mosca; Guidoni, Leonardo

doi:10.1016/j.comptc.2014.03.011

Cited by 29 publications

(51 citation statements)

References 81 publications

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“…), but the computational requirements concomitantly become so high that only small compounds can still be treated. Another alternative to TD‐DFT is BSE/ GW that similarly to DFT comes from solid state physics, but is now increasingly popular for molecular systems . Some benchmarks have pointed out an enhanced accuracy of BSE/ GW compared to TD‐DFT, despite the same

scriptO ((), N^{4})

scaling with system size.…”

Section: Discussionmentioning

confidence: 99%

Going beyond the vertical approximation with time‐dependent density functional theory

Santoro

Jacquemin

2016

WIREs Comput Mol Sci

190

229

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Since two decades, time-dependent density functional theory (TD-DFT) has been in the limelight due to its noteworthy efficiency. Indeed, in many cases, TD-DFT provides accurate excited-state properties for a relatively limited computational cost. Recently, there has been a rapidly growing interest in applications of TD-DFT (partly) exploring the excited-state potential energy surfaces. In this review, we summarize such TD-DFT investigations going beyond the vertical approximation and devoted to spectroscopic applications, with a focus on both 0-0 energies and vibrationally resolved absorption and emission spectra. We show how these quantities can be computed, considering various models for the latter, and illustrate their advantages compared to vertical estimates in terms of comparisons with experimental data.

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scriptO ((), N^{4})

scaling with system size.…”

Section: Discussionmentioning

confidence: 99%

Going beyond the vertical approximation with time‐dependent density functional theory

Santoro

Jacquemin

2016

WIREs Comput Mol Sci

190

229

View full text Add to dashboard Cite

show abstract

“…[16][17][18] Recently, the use of many-body Green's functions theory, 15,[19][20][21] typically more rooted in the solid-state community, has received increasing attention in quantumchemical applications. [22][23][24][25][26][27][28][29][30][31][32][33] It consists of a two-step procedure, in which at first the addition and removal of an electron is calculated within the GW approximation as quasiparticle excitations to an N -electron (DFT) ground state. In the second step, neutral excitations are constructed in the same framework as coupled electron-hole pairs by solving the so-called Bethe-Salpeter Equation (BSE).…”

Section: Introductionmentioning

confidence: 99%

Excited-state electronic structure of molecules using many-body Green’s functions: Quasiparticles and electron–hole excitations with VOTCA-XTP

Tirimbó

Sundaram

Çaylak

et al. 2020

The Journal of Chemical Physics

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We present the open-source VOTCA-XTP software for the calculation of the excited-state electronic structure of molecules using many-body Green's functions theory in the GW approximation with the Bethe-Salpeter Equation (BSE). This work provides a summary of the underlying theory and discusses details of its implementation based on Gaussian orbitals, including, i.a., resolution-of-identity techniques, different approaches to the frequency integration of the self-energy or acceleration by offloading compute-intensive matrix operations using GPUs in a hybrid OpenMP/Cuda scheme. A distinctive feature of VOTCA-XTP is the capability to couple the calculation of electronic excitations to a classical polarizable environment on atomistic level in a coupled quantum-and molecular-mechanics (QM/MM) scheme, where a complex morphology can be imported from Molecular Dynamics simulations. The capabilities and limitations of the GW -BSE implementation are illustrated with two examples. First, we study the dependence of optically active electron-hole excitations in a series of diketopyrrolopyrrole-based oligomers on molecular-architecture modifications and the number of repeat units. Second, we use the GW -BSE/MM setup to investigate the effect of polarization on localized and intermolecular charge-transfer excited states in morphologies of low-donor content rubrenefullerene mixtures. These showcases demonstrate that our implementation currently allows to treat systems with up to 2500 basis functions on regular shared-memory workstations, providing accurate descriptions of quasiparticle and coupled electron-hole excited states of various character on an equal footing.

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“…66 As another direction of progress, GW and BSE calculations were recently achieved starting from eigenstates generated with a QM/MM approach at the DFT level, namely ground-state polarization effects were introduced, but the excitations out of the groundstate were not screened. 67,68 Finally, a polarizable model with a regular grid of polarizable centres was recently combined with the GW and BSE formalisms for the study of Frenkel and charge-transfer excitations in a donor/acceptor complex. 45 In the present study, we explore the merits of combining the GW formalism with the polarizable continuum model.…”

Section: Introductionmentioning

confidence: 99%

Combining the GW formalism with the polarizable continuum model: A state-specific non-equilibrium approach

Duchemin

Jacquemin

Blase

2016

The Journal of Chemical Physics

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We have implemented the polarizable continuum model within the framework of the many-body Green's function GW formalism for the calculation of electron addition and removal energies in solution. The present formalism includes both ground-state and non-equilibrium polarization effects. In addition, the polarization energies are state-specific, allowing to obtain the bath-induced renormalisation energy of all occupied and virtual energy levels. Our implementation is validated by comparisons with ΔSCF calculations performed at both the density functional theory and coupled-cluster single and double levels for solvated nucleobases. The present study opens the way to GW and Bethe-Salpeter calculations in disordered condensed phases of interest in organic optoelectronics, wet chemistry, and biology.

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Ground state structures and electronic excitations of biological chromophores at Quantum Monte Carlo/Many Body Green’s Function Theory level

Cited by 29 publications

References 81 publications

Going beyond the vertical approximation with time‐dependent density functional theory

Going beyond the vertical approximation with time‐dependent density functional theory

Excited-state electronic structure of molecules using many-body Green’s functions: Quasiparticles and electron–hole excitations with VOTCA-XTP

Combining the GW formalism with the polarizable continuum model: A state-specific non-equilibrium approach

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