Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 3, Issue 18, Pages 2726-2732Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jz3011139
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Funding
- National Science Foundation [CHE-0951634]
- Bessel Research Award from the Humboldt Foundation
- Dornsife College of Letters, Arts, and Sciences
- WISE program (USC) for bridge
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0951634] Funding Source: National Science Foundation
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Benchmark calculations of the lowest ionized state of the (A:T)(2) (mixed adenine thymine) cluster at the geometry taken from the DNA X-ray structure are presented. Vertical ionization energies (IEs) computed by the equation-of-motion coupled-cluster method with single and double substitutions are reported and analyzed. The shift in IE relative to the monomer (A) is -0.7 eV. The performance of the widely used B3LYP, omega B97X-D, and M06-2X functionals with respect to their ability to describe energetics and the character (localization versus delocalization) of the ionized states is also investigated. The shifts in IEs caused by H-bonding and stacking interactions are analyzed in terms of additive versus cooperative effects. It is found that the cooperative effect accounts for more than 20% of the shift in IE relative to the monomer. The cooperative effect and, consequently, the magnitude of the shift are well reproduced by the hybrid quantum mechanics/molecular mechanics scheme in which neutral thymine bases are represented by point charges.
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