Electron/Hole Mobilities of Periodic DNA and Nucleobase Structures from Large-Scale DFT Calculations
[1];
[4]
- Materials Science Division, Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, California 94550, United States
- Materials Science & Engineering Program, University of California-Riverside, 900 University Drive, Riverside, California 92521, United States
- Applied Mathematics & Computational Research Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States
- Materials Science & Engineering Program, University of California-Riverside, 900 University Drive, Riverside, California 92521, United States, Department of Chemistry and Department of Physics & Astronomy, University of California-Riverside, 900 University Drive, Riverside, California 92521, United States
Electron/hole transfer mechanisms in DNA and polynucleotide structures continue to garner considerable interest as emerging charge-transport systems and molecular electronics. To shed mechanistic insight into these electronic properties, we carried out large-scale density functional theory (DFT) calculations (up to 650 atoms) to systematically analyze the structural and electron/hole transport properties of fully periodic single- and double-stranded DNA. We examined the performance of various exchange–correlation functionals (LDA, BLYP, B3LYP, and B3LYP-D) and found that single-stranded thymine (T) and cytosine (C) are predominantly hole conductors, whereas single-stranded adenine (A) and guanine (G) are better electron conductors. For double-stranded DNA structures, the periodic A-T and G-C electronic band structures undergo a significant renormalization, which causes hole transport to only occur on the A and G nucleobases. Our calculations (1) provide new benchmarks for periodic nucleobase structures using dispersion-corrected hybrid functionals with large basis sets and (2) highlight the importance of dispersion effects for obtaining accurate geometries and electron/hole mobilities in these extended systems.
- Research Organization:
- Univ. of California, Riverside, CA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR). Scientific Discovery through Advanced Computing (SciDAC)
- Grant/Contract Number:
- SC0022209
- OSTI ID:
- 1986368
- Alternate ID(s):
- OSTI ID: 1988232
- Journal Information:
- Journal of Physical Chemistry. B, Journal Name: Journal of Physical Chemistry. B Vol. 127 Journal Issue: 26; ISSN 1520-6106
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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