Jump to main content
Jump to site search

Issue 6, 2015
Previous Article Next Article

Applicability of optimal functional tuning in density functional calculations of ionization potentials and electron affinities of adenine–thymine nucleobase pairs and clusters

Author affiliations

Abstract

The intrinsic properties of DNA and RNA nucleic acid bases (NABs) such as ionization potentials (IPs) and electron affinities (EAs) are crucial to reveal various biochemical mechanisms. Successful application of density functional theory (DFT) using nonempirically tuned long-range corrected (LC) functionals for calculation of vertical ionization potentials (VIPs) and electron affinities (VEAs) of various adenine–thymine (AT) nucleobase pairs and clusters is demonstrated. We employ a tuning method by applying an asymptotically correct exchange–correlation potential adjusted to give frontier orbital energies (−εHOMO and −εLUMO) representing IPs and EAs and assess the quality of prediction which is comparable to high-level EOM-IP-CCSD/CCSD methods. The delocalization error calculated using different DFT functionals is quantified by calculations using fractional electron numbers. The cooperative effect of H-bonding and π-stacking on the IPs of AT clusters, as well as the reactivity parameters (global hardness and electrophilicity), is quantitatively characterized using the tuned LC functionals. The present work aims at providing a reliable and efficient theoretical tool for the prediction of the related electron donor and acceptor abilities of the NAB systems.

Graphical abstract: Applicability of optimal functional tuning in density functional calculations of ionization potentials and electron affinities of adenine–thymine nucleobase pairs and clusters

Back to tab navigation

Supplementary files

Article information


Submitted
24 Nov 2014
Accepted
02 Jan 2015
First published
02 Jan 2015

Phys. Chem. Chem. Phys., 2015,17, 4337-4345
Article type
Paper
Author version available

Applicability of optimal functional tuning in density functional calculations of ionization potentials and electron affinities of adenine–thymine nucleobase pairs and clusters

H. Sun, S. Zhang and Z. Sun, Phys. Chem. Chem. Phys., 2015, 17, 4337
DOI: 10.1039/C4CP05470A

Social activity

Search articles by author

Spotlight

Advertisements