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

Abstract

The photoelectron properties of DNA and RNA bases are studied using many-body perturbation theory within the GW approximation, together with a recently developed Lanczos-chain approach. Calculated vertical ionization potentials, electron affinities, and total density of states are in good agreement with experimental values and photoemission spectra. Convergence benchmark demonstrates the importance of using an optimal polarizability basis in the GW calculations. A detailed analysis of the role of exchange and correlation in both many-body and density-functional theory calculations shows that while self-energy corrections are strongly orbital-dependent, they nevertheless remain almost constant for states that share the same bonding character. Finally, we report on the inverse lifetimes of DNA and RNA bases, that are found to depend linearly on quasi-particle energies for all deep valence states. In general, our G0W0-Lanczos approach provides an efficient yet accurate and fully-converged description of quasiparticle properties of five DNA and RNA bases.

First-principles investigation of organic photovoltaic materialsC60, C70, [C60]PCBM, and bis-Qian1, Umari2, Marzari3 2015Phys. Rev. BSelf Cite

“…As listed in Table I for C 60 , the quantitative description of quasiparticle energies at the G 0 W 0 level can be improved by solving the bottleneck of the sum-over-emptystates through the efficient Lanczos approach [69][70][71][72][73] We display in Figs. 2 and 3 the electronic density of states (DOS) of the five electron-acceptor molecules, calculated with G 0 W 0 @LDA and G 0 W 0 @GGA, respectively, and compare them with direct and inverse photoemission data without peak alignment, albeit neglecting any oscillator strength effect in the calculation.…”

“…The GW method has already been applied to fullerenes in some theoretical works [66][67][68] . Here, we use the recently developed many-body GW-Lanczos approach which is particularly effective in reaching numerical convergence [69][70][71][72][73] in large atomic structures without suffering from bottlenecks with respect to summing over a large number of empty Kohn-Sham orbitals. This allows us to calculate the electronic structure of the electron acceptors including C 60 , C 70 , [C 60 ]PCBM, and bis-[C 60 ]PCBM at both the DFT and GW level, and compare them with experimental photoemission results.…”

Benchmark ofGWmethods for azabenzenes

“…1, [30][31][32][33][34][35][36][37][38][39][40][41][42] ) and has had some notable success in the description of the electronic structure of various organic 10,13,[43][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59][60] and metal-organic molecules, 59, 61 as well as organic-inorganic interfaces. [8][9][10][11][12][13][14][15][16] However, the non-self-consistency gives rise to a dependence of the G 0 W 0 results on the DFT starting point.…”

First-Principles Photoemission Spectroscopy of DNA and RNA Nucleobases from Koopmans-Compliant Functionals

“…The same issue affects GW calculations when they are performed with localized basis sets 59 , while it does not apply to plane-wave-based GW methods. Indeed Qian, Umari and Marzari 11 were able to obtain an empty VB state with negative energy (positive binding energy, thus able to bind an extra electron) in the spectrum of neutral guanine.…”

“…Extensive studies to understand the electronic properties of nucleobases have been carried out for many years, both theoretically and experimentally [2][3][4][5][6][7][8][9][10][11][12][13] . Notwithstanding such efforts, many questions related to photoelectron properties, such as the stability and symmetry of ionized states, are yet to be understood 5,14 .…”