Reply to Comment on 'Excited states of DNA base pairs using long-range corrected time-dependent density functional theory

Journal Article · Fri Sep 18 00:00:00 EDT 2009 · Journal of Physical Chemistry A, 113(41):11095

DOI:https://doi.org/10.1021/jp908490z· OSTI ID:993358

Jensen, Lasse; Govind, Niranjan

In this work we present a study of the excitation energies of adenine, cytosine, guanine, thymine and the adenine-thymine (AT) and guanine-cytosine (GC) base pairs using long-range corrected (LC) density functional theory. We compare three recent LC-functionals, BNL, CAM-B3LYP and LC-PBE0 with B3LYP and coupled cluster results from the literature. We find that the best overall performance is for the BNL functional based on LDA. However, in order to achieve this good agreement a smaller attenuation parameter was needed which leads to non-optimum performance for ground state properties. B3LYP, on the other hand, severely underestimates the charge transfer (CT) transitions in the base pairs. Surprisingly we also find that the CAM-B3LYP functional also underestimates the CT excitation energy for the GC base pair, but correctly describes the AT base pair. This illustrates the importance of retaining the full long-range exact exchange even at distances as short as that of the DNA base pairs. The worst overall performance was obtained with the LC-PBE0 functional which overestimates the excitations for the individual bases as well as the base pairs. It is therefore crucial to strike a good balance between the amount of local and long-range exact exchange.

• Research Organization: Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 993358
• Report Number(s): PNNL-SA-69344; JPCAFH; 29790; KP1704020; TRN: US201023%%296
• Journal Information: Journal of Physical Chemistry A, 113(41):11095, Vol. 113, Issue 41; ISSN 1089-5639
• Country of Publication: United States
• Language: English

Related Subjects

59 BASIC BIOLOGICAL SCIENCES
99 GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE
ATTENUATION
BNL
CYTOSINE
DNA
EXCITATION
FUNCTIONALS
GROUND STATES
GUANINE
PERFORMANCE
THYMINE
time-dependent density functional theory
excitation
energies
Environmental Molecular Sciences Laboratory