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TheoreticalBackground
2.6 ChargeTransfer inDNA
In this chapter, a short introduction into the basics of charge transfer and the
needed parameters is given. Then, two advanced methods for the propagation
of thewave-functionof the excess chargewill be summarized. This represents the
rather chemical point of view of a charge transfer process, where the charge re-
sides on onemolecule, or part of themolecule, and then is transferred to another
molecule. Two of these non-adiabatic methods were implemented in our frame-
workandrecentlypublished[72,73].
2.6.1 BasicsofChargeTransfer
The classical way to the CT in complexmolecular systems isMarcus’ theory [71,
85] and its extensions [86–90] Here, a rate of transfer between a donor and an
acceptor for the non-adiabatic case can be calculated from several charge transfer
parameters.
kDA= |VDA|2
h¯ √
π
λkBT exp [
−(ΔG 0+λ)2
4λkBT ]
(2.36)
Theseparameters are:
• the electronic coupling (EC) |VDA|2 between thedonorand theacceptor
• the reaction free energyΔGof theCTprocess
• and the reorganizationenergy (RE)λ
All three can be obtained using various computationalmethods. The static elec-
tronic couplings can be calculated with highly accurate quantum chemical (QC)
methods likeCAS-PT2.Moreefficientmethodshave tobeused tocalculate thedy-
namicelectroniccouplings in thecourseofanMDsimulation. Inourapproach, the
dynamicECareobtainedusingtheDFTB2method(seesection2.3.2 fordetails)and
a fragment orbital approach[91]. ΔG andλ are thermodynamic quantities, so that
their computationcanbedonebysamplingof theconfigurationspace, e.g. freeen-
ergy calculations. TheRE is the energyneeded to reorient themolecules and their
environmenttotheconformationcorrespondingtothefinalstateof theCTreaction.
32
Charge Transport in DNA
Insights from Simulations
- Title
- Charge Transport in DNA
- Subtitle
- Insights from Simulations
- Author
- Mario Wolter
- Publisher
- KIT Scientific Publishing
- Date
- 2013
- Language
- English
- License
- CC BY-SA 3.0
- ISBN
- 978-3-7315-0082-7
- Size
- 17.0 x 24.0 cm
- Pages
- 156
- Keywords
- Charge Transport, Charge Transfer, DNA, Molecular Dynamics, Quantum Mechanics
- Categories
- Naturwissenschaften Chemie
Table of contents
- Zusammenfassung 1
- Summary 3
- 1 Introduction 5
- 2 TheoreticalBackground 11
- 3 SimulationSetup 39
- 4 DNAUnderExperimentalConditions 49
- 5 ChargeTransport inStretchedDNA 69
- 6 ChargeTransport inMicrohydratedDNA 79
- 7 AParametrizedModel toSimulateCT inDNA 89
- 8 Conclusion 105
- Appendix 111
- A DNAUnderExperimentalConditions 111
- B CTinMicrohydratedDNA 117
- List ofPublications 137