First-principlesGWcalculations for DNA and RNA nucleobases

Photoelectron properties of DNA and RNA bases from many-body perturbation theory

“…Photoelectron properties of DNA and RNA bases using many-body GW have not been reported until a very recent study by Faber et al 33 . The work by Faber et al presents a many-body GW study on QP energies (including ionization potentials and electron affinities) of DNA and RNA bases at several levels of self-consistency within the GW approximation.…”

“…In contrast, manybody perturbation theory within Hedin's GW approximation 16,17 presents a unique framework that allows access to both quasi-particle (QP) energies and lifetimes on the same footing. This method has been successfully applied to quasi-1D, 2D and 3D semiconductors, insulators, and metals [18][19][20][21][22][23] , and very recently to molecular systems [24][25][26][27][28][29][30][31][32][33] .…”

Ionization Energies, Electron Affinities, and Polarization Energies of Organic Molecular Crystals: Quantitative Estimations from a Polarizable Continuum Model (PCM)-Tuned Range-Separated Density Functional Approach

“…18,[21][22][23][24] However, not only is GW computationally much more demanding than DFT, the fact that it is typically employed non-self-consistently also leads to a significant starting-point dependence. [25][26][27][28][29][30][31] For the case of the pentacene molecule, for example, it has been found that nonself-consistent G 0 W 0 calculations based on a (semi-)local DFT starting point underestimate the fundamental gap E g in the gas phase by as much as 0.7 eV, while E g calculated at the same level of theory for the pentacene crystal are found in good agreement with the experimentally determined solid-state E g , likely due to a fortuitous cancelation of errors. 18 The G 0 W 0 accuracy can be significantly improved by the introduction of self-consistency at the level of eigenvalues 26,32 or using "better" DFT starting points such as the global hybrid PBE0, 27,28,33 short-range hybrid Heyd-Scuseria-Ernzerhof (HSE) functionals, 18 as well as standard 33 and nonempirically tuned long-range corrected hybrid functionals.…”

“…[25][26][27][28][29][30][31] For the case of the pentacene molecule, for example, it has been found that nonself-consistent G 0 W 0 calculations based on a (semi-)local DFT starting point underestimate the fundamental gap E g in the gas phase by as much as 0.7 eV, while E g calculated at the same level of theory for the pentacene crystal are found in good agreement with the experimentally determined solid-state E g , likely due to a fortuitous cancelation of errors. 18 The G 0 W 0 accuracy can be significantly improved by the introduction of self-consistency at the level of eigenvalues 26,32 or using "better" DFT starting points such as the global hybrid PBE0, 27,28,33 short-range hybrid Heyd-Scuseria-Ernzerhof (HSE) functionals, 18 as well as standard 33 and nonempirically tuned long-range corrected hybrid functionals. 30,34 However, the application of hybrid functionals for periodic systems is still computationally demanding, in particular when using the large basis sets required to converge a G 0 W 0 calculation.…”

Quasi-particle energy spectra in local reduced density matrix functional theory

“…The Perdew-Zunger self-interaction correction (SIC) method 17 in DFT offers a correction to this problem and was found to yield orbital energies closer to the experimental IPs 18 improving several other properties as well. [18][19][20] The GW method [21][22][23] was initially introduced to improve the obtained quasiparticle spectrum of solids but in the last decade, GW at various levels of approximations was also applied to finite systems [24][25][26][27][28][29][30] improving significantly the quasiparticle excitation energies with respect to standard DFT-approximations. Those calculations suffer from a strong initial state dependence and the good agreement found could be just fortuitous.…”