Reorganization energy, activation energy, and mechanism of hole transfer process in DNA: A theoretical study

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Abstract

The density functional calculations with aug-cc-pVDZ basis sets on cationic guanine-cytosine (GC+) and adenine-thymine (AT+) base pairs suggest that the cationic charge is almost entirely localized on the G and A units with significant changes in the N-H and NO distances around the H-bonded area. While the calculated intramolecular reorganization energy (λv) for a GC base pair (0.75 eV) is remarkably larger than that for an isolated G base (0.49 eV), for the AT base pairs these values (0.44 and 0.40 eV) are almost the same. The gas phase activation energies (Ea) for GC+ GC→ GCGC+, AT+ AT→ ATAT+, and GC+ AT→ GCAT+ hole transfer processes are 0.19, 0.11, and 0.73 eV with rate constants of 1.69× 1011, 3.15× 1011, and 4.61 (0.168) s-1, respectively, at 298 K. An alternative mechanism of hole transfer has been proposed on the basis of energy barriers.

Original languageEnglish (US)
Article number075101
JournalJournal of Chemical Physics
Volume128
Issue number7
DOIs
StatePublished - Mar 3 2008

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Thymine
Cytosine
Energy barriers
Guanine
Adenine
Density functional theory
Rate constants
deoxyribonucleic acid
Activation energy
Gases
activation energy
DNA
thymine
guanines
adenines
energy
vapor phases
Aeromonas hydrophilia lipase-acyltransferase

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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title = "Reorganization energy, activation energy, and mechanism of hole transfer process in DNA: A theoretical study",
abstract = "The density functional calculations with aug-cc-pVDZ basis sets on cationic guanine-cytosine (GC+) and adenine-thymine (AT+) base pairs suggest that the cationic charge is almost entirely localized on the G and A units with significant changes in the N-H and NO distances around the H-bonded area. While the calculated intramolecular reorganization energy (λv) for a GC base pair (0.75 eV) is remarkably larger than that for an isolated G base (0.49 eV), for the AT base pairs these values (0.44 and 0.40 eV) are almost the same. The gas phase activation energies (Ea) for GC+ GC→ GCGC+, AT+ AT→ ATAT+, and GC+ AT→ GCAT+ hole transfer processes are 0.19, 0.11, and 0.73 eV with rate constants of 1.69× 1011, 3.15× 1011, and 4.61 (0.168) s-1, respectively, at 298 K. An alternative mechanism of hole transfer has been proposed on the basis of energy barriers.",
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AU - Khan, Arshad

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N2 - The density functional calculations with aug-cc-pVDZ basis sets on cationic guanine-cytosine (GC+) and adenine-thymine (AT+) base pairs suggest that the cationic charge is almost entirely localized on the G and A units with significant changes in the N-H and NO distances around the H-bonded area. While the calculated intramolecular reorganization energy (λv) for a GC base pair (0.75 eV) is remarkably larger than that for an isolated G base (0.49 eV), for the AT base pairs these values (0.44 and 0.40 eV) are almost the same. The gas phase activation energies (Ea) for GC+ GC→ GCGC+, AT+ AT→ ATAT+, and GC+ AT→ GCAT+ hole transfer processes are 0.19, 0.11, and 0.73 eV with rate constants of 1.69× 1011, 3.15× 1011, and 4.61 (0.168) s-1, respectively, at 298 K. An alternative mechanism of hole transfer has been proposed on the basis of energy barriers.

AB - The density functional calculations with aug-cc-pVDZ basis sets on cationic guanine-cytosine (GC+) and adenine-thymine (AT+) base pairs suggest that the cationic charge is almost entirely localized on the G and A units with significant changes in the N-H and NO distances around the H-bonded area. While the calculated intramolecular reorganization energy (λv) for a GC base pair (0.75 eV) is remarkably larger than that for an isolated G base (0.49 eV), for the AT base pairs these values (0.44 and 0.40 eV) are almost the same. The gas phase activation energies (Ea) for GC+ GC→ GCGC+, AT+ AT→ ATAT+, and GC+ AT→ GCAT+ hole transfer processes are 0.19, 0.11, and 0.73 eV with rate constants of 1.69× 1011, 3.15× 1011, and 4.61 (0.168) s-1, respectively, at 298 K. An alternative mechanism of hole transfer has been proposed on the basis of energy barriers.

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