First-Principles Photoemission Spectroscopy of DNA and RNA Nucleobases from Koopmans-Compliant Functionals.
The need to interpret ultraviolet photoemission data strongly motivates the refinement of first-principles techniques that are able to accurately predict spectral properties. In this work, we employ Koopmans-compliant functionals, constructed to enforce piecewise linearity in approximate density functionals, to calculate the structural and electronic properties of DNA and RNA nucleobases. Our results show that not only ionization potentials and electron affinities are accurately predicted with mean absolute errors of <0.1 eV, but also that calculated photoemission spectra are in excellent agreement with experimental ultraviolet photoemission spectra. In particular, the role and contribution of different tautomers to the photoemission spectra are highlighted and discussed in detail. The structural properties of nucleobases are also investigated, showing an improved description with respect to local and semilocal density-functional theory. Methodologically, our results further consolidate the role of Koopmans-compliant functionals in providing, through orbital-density-dependent potentials, accurate electronic and spectral properties.
Theory and Simulations of Materials (THEOS) and National Centre for Computational Design and Discovery of Novel Materials (MARVEL), École Polytechnique Fédérale de Lausanne , 1015 Lausanne, Switzerland.
Ngoc Linh
NL
Nguyen
Theory and Simulations of Materials (THEOS) and National Centre for Computational Design and Discovery of Novel Materials (MARVEL), École Polytechnique Fédérale de Lausanne , 1015 Lausanne, Switzerland.|Centro S3, CNR-Istituto Nanoscienze , 41125 Modena, Italy.
Giovanni
G
Borghi
Centro S3, CNR-Istituto Nanoscienze , 41125 Modena, Italy.
Andrea
A
Ferretti
Theory and Simulations of Materials (THEOS) and National Centre for Computational Design and Discovery of Novel Materials (MARVEL), École Polytechnique Fédérale de Lausanne , 1015 Lausanne, Switzerland.
Nicola
N
Marzari
D004247:DNA / Q000737:chemistry*; D009690:Nucleic Acid Conformation; D009705:Nucleosides / Q000737:chemistry*; D056951:Photoelectron Spectroscopy; D011789:Quantum Theory; D012313:RNA / Q000737:chemistry*
D009705:Nucleosides; D012313:RNA; D004247:DNA