Non-Empirically Tuned Range-Separated DFT Accurately Predicts Both Fundamental and Excitation Gaps in DNA and RNA Nucleobases

Abstract

Using a non-empirically tuned range-separated DFT approach, we study both the quasiparticle properties (HOMO-LUMO fundamental gaps) and excitation energies of DNA and RNA nucleobases (adenine, thymine, cytosine, guanine, and uracil). Our calculations demonstrate that a physically-motivated, first-principles tuned DFT approach accurately reproduces results from both experimental benchmarks and more computationally intensive techniques such as many-body GW theory. Furthermore, in the same set of nucleobases, we show that the non-empirical range-separated procedure also leads to significantly improved results for excitation energies compared to conventional DFT methods. The present results emphasize the importance of a non-empirically tuned range-separation approach for accurately predicting both fundamental and excitation gaps in DNA and RNA nucleobases.

Accepted by the Journal of Chemical Theory and Computation

References in corpus (4)

• Optoelectronic and Excitonic Properties of Oligoacenes: Substantial Improvements from Range-Separated Time-Dependent Density Functional Theory
• First-principles GW calculations for DNA and RNA nucleobases
• Coumarin Dyes for Dye-Sensitized Solar Cells - A Long-Range-Corrected Density Functional Study
• Electronically Excited States of Vitamin B12: Benchmark Calculations Including Time-Dependent Density Functional Theory and Correlated Ab Initio Methods

Cited by in corpus (18)

• Charge-Transfer in Time-Dependent Density Functional Theory
• Halogen Bonding Interactions: Revised Benchmarks and a New Assessment of Exchange vs. Dispersion
• Accurate Electron Affinities and Orbital Energies of Anions from a Non-Empirically Tuned Range-Separated Density Functional Theory Approach
• Tuning Range-Separated Density Functional Theory for Photocatalytic Water Splitting Systems
• Experimental and theoretical electronic structure of quinacridone
• Structural and Electronic Properties of Graphdiyne Carbon Nanotubes from Large-Scale DFT Calculations
• The Importance of Short- and Long-Range Exchange on Various Excited State Properties of DNA Monomers, Stacked Complexes, and Watson-Crick Pairs
• A self-interaction-free local hybrid functional: Accurate binding energies vis-à-vis accurate ionization potentials from Kohn-Sham eigenvalues
• Charge-Transfer Matrix Elements by FMO-LCMO Approach: Hole Transfer in DNA with Parameter Tuned Range-Separated DFT
• Quasiparticle band structures, spontaneous polarization, and spin-splitting in noncentrosymmetric few-layer and bulk $\gamma$-GeSe
• Improvements in the orbitalwise scaling down of Perdew-Zunger self-interaction correction in many-electron regions
• Charge Density Wave Hampers Exciton Condensation in 1T-TiSe${}_2$
• PAMELA: An Open-Source Software Package for Calculating Nonlocal Exact Exchange Effects on Electron Gases in Core-Shell Nanowires
• Nonadiabatic Time-Dependent Spin-Density Functional Theory for strongly correlated systems
• Computational Design of Crescent Shaped Promising NonFullerene Acceptors with 2,3-quinoxaline,1,4-dihydro Core and Different Electron-withdrawing Terminal Units for Photovoltaic Applications
• Porous carbon nitride fullerenes: a novel family of porous cage molecules
• Nature of frontier quasi-particle states in nitrogen-base systems
• Quantum Study of Dispersion-Corrected Electronic and Optical Properties of syn- and anti- B18H22 Clusters with/without Sulfur Doping for Tunable Optoelectronics