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Modelling charge transfer reactions with the frozen density embedding formalism
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10.1063/1.3666005
/content/aip/journal/jcp/135/23/10.1063/1.3666005
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/23/10.1063/1.3666005

Figures

Image of FIG. 1.
FIG. 1.

Spin densities (contour at ±10−4 bohr−3) of a guanine-cytosine dimer radical cation, . Inset (a) from a supermolecular calculation; inset (b) FDE(m) with two subsystems: left GC is positively charged, while the density of the GC on the right is let integrate to neutrality; inset (c) FDE(m) with four subsystems: left guanine is positively charged, the other three subsystems are neutral and are composed of left cytosine, right guanine, and right cytosine. In all cases, three freeze and thaw cycles have been performed for all densities.

Image of FIG. 2.
FIG. 2.

Structures of the model systems chosen. (GG)+ in inset (a) and (GT)+ in inset (b). The Cartesian coordinates were taken from Ref. 53. Grey: carbons; white: hydrogens; blue: nitrogens; and red: oxygens.

Image of FIG. 3.
FIG. 3.

Calculated electronic coupling, H 12 in eV, for the hole transfer in 5-GG-3 (black, squares) and 5-GT-3 (red, circles) base stacks versus the percentage of exact exchange employed in the DFT functional. All data are taken from Tables V and VI. In overlay dashed lines reporting the CASPT2 benchmark values taken from Ref. 53. Couplings are given in units of eV.

Tables

Generic image for table
Table I.

Calculated donor-acceptor electrostatic (el) and non-additive (nadd) contributions to the interaction energies calculated with Eq. (8) for the hole transfer in a 5-GG-3 base stack from regular B-DNA (atomic coordinates taken from Ref. 53) employing several DFT functionals in the evaluation of v KS in the embedding calculations. All calculations were performed with the standard TZP basis set. All the energy quantities are given in eV.

Generic image for table
Table II.

Calculated donor-acceptor electrostatic (el) and non-additive (nadd) contributions to the interaction energies calculated with Eq. (8) for the hole transfer in a 5-GT-3 base stack from regular B-DNA (atomic coordinates taken from Ref. 53) employing several DFT functionals in the evaluation of v KS in the embedding calculations. All calculations were performed with the standard TZP basis set. All the energy quantities are given in eV.

Generic image for table
Table III.

Calculated donor-acceptor Kohn–Sham (KS), electrostatic (el), and non-additive (nadd) energy contributions to the energy differences for the hole transfer in a 5-GG-3 base stack from regular B-DNA, see the caption of Table I for details. All values are in eV.

Generic image for table
Table IV.

Calculated donor–acceptor Kohn–Sham (KS), electrostatic (el), and non-additive (nadd) energy contributions to the charge–localized energy differences for the hole transfer in a 5-GT-3 base stack from regular B-DNA, see the caption to Table I for details. All values in eV.

Generic image for table
Table V.

Calculated electronic coupling for the hole transfer in a 5-GG-3 base stack from regular B-DNA (atomic coordinates taken from Ref. 53) employing several DFT functionals in the embedding and supermolecular calculations. All calculations were performed with the standard TZP basis set. All the energy quantities are given in eV. The table features the overlap between non-orthogonal FDE charge-localized states, ; the overlaps between non-orthogonal FDE charge-localized states and the ground state KS determinant, A and B, respectively; the electronic coupling calculated with, and without the non-additive kinetic energy and exchange-correlation contributions to the charge-localized energy, H 12 and , respectively; the percent deviation of H 12 and is collected in the column labelled with “QM-el %.” CASSCF(11,12) and CASPT2(11,12) benchmark values are taken from Ref. 53.

Generic image for table
Table VI.

Calculated electronic coupling for the hole transfer in a 5-GT-3 DNA base stack. See caption of Table V for details. All energy values are in eV.

Generic image for table
Table VII.

Calculated adiabatic excitation energy of the first CT excited state for the hole transfer in a 5-GG-3 and 5-GT-3 base stacks. Benchmark values at the bottom of the table calculated with a 6-31G* basis set. See caption of Table V for details. Values are in eV.

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/content/aip/journal/jcp/135/23/10.1063/1.3666005
2011-12-16
2014-04-18
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Modelling charge transfer reactions with the frozen density embedding formalism
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/23/10.1063/1.3666005
10.1063/1.3666005
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