### Abstract

Charge transfer (CT) stabilization in linear stacks D+A-D+A- of -electron donors (D) and acceptors (A) involve spin-dependent configuration interactions that are treated exactly in rings of N=4, 6, 8, 10 sites, and extrapolated to N, by adapting valence-bond techniques to electron-hole excitations. The ground state CT (z) and the magnetic gap Em(z)2|t| to the lowest triplet are computed for arbitrary z=2|t|, where -2 is the energy for DAD+A-, -|t|=D+A-|H|DA is the Mulliken CT integral, and D2+, A2- sites are excluded. The spin degeneracy of A- and D+ ion radicals is treated exactly. Instead of the discontinuous change from =0 to =1 in the limit |t|0, finite overlap gives a continuous (z) and (zc)=0.680.01 at the neutral-ionic interface zc=0.530.01. The magnetic gap Em is finite for z<zc and vanishes for z>zc, where there is a diamagnetic to paramagnetic transition and the ground state switches from k=0 to k= symmetry. Collective effects due to long-range three-dimensional Coulomb interactions are included in a Hartree approximation and produce a first-order transition, with discontinuous (z), when the critical value m2|t|=1.40.1 of the Madelung stabilization m of a dimer is exceeded. The puzzling magnetic gaps in paramagnetic organic CT salts with mixed regular stacks arise naturally for partial CT and z<zc. Valence-bond analysis of CT excitations models the physical properties of organic complexes with overlapping sites and intermediate.

Original language | English (US) |
---|---|

Pages (from-to) | 1991-2003 |

Number of pages | 13 |

Journal | Physical Review B |

Volume | 18 |

Issue number | 4 |

DOIs | |

State | Published - 1978 |

Externally published | Yes |

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### ASJC Scopus subject areas

- Condensed Matter Physics

### Cite this

*Physical Review B*,

*18*(4), 1991-2003. https://doi.org/10.1103/PhysRevB.18.1991

**Neutral-ionic interface in organic charge-transfer salts.** / Soos, Z. G.; Mazumdar, Sumitendra.

Research output: Contribution to journal › Article

*Physical Review B*, vol. 18, no. 4, pp. 1991-2003. https://doi.org/10.1103/PhysRevB.18.1991

}

TY - JOUR

T1 - Neutral-ionic interface in organic charge-transfer salts

AU - Soos, Z. G.

AU - Mazumdar, Sumitendra

PY - 1978

Y1 - 1978

N2 - Charge transfer (CT) stabilization in linear stacks D+A-D+A- of -electron donors (D) and acceptors (A) involve spin-dependent configuration interactions that are treated exactly in rings of N=4, 6, 8, 10 sites, and extrapolated to N, by adapting valence-bond techniques to electron-hole excitations. The ground state CT (z) and the magnetic gap Em(z)2|t| to the lowest triplet are computed for arbitrary z=2|t|, where -2 is the energy for DAD+A-, -|t|=D+A-|H|DA is the Mulliken CT integral, and D2+, A2- sites are excluded. The spin degeneracy of A- and D+ ion radicals is treated exactly. Instead of the discontinuous change from =0 to =1 in the limit |t|0, finite overlap gives a continuous (z) and (zc)=0.680.01 at the neutral-ionic interface zc=0.530.01. The magnetic gap Em is finite for zzc, where there is a diamagnetic to paramagnetic transition and the ground state switches from k=0 to k= symmetry. Collective effects due to long-range three-dimensional Coulomb interactions are included in a Hartree approximation and produce a first-order transition, with discontinuous (z), when the critical value m2|t|=1.40.1 of the Madelung stabilization m of a dimer is exceeded. The puzzling magnetic gaps in paramagnetic organic CT salts with mixed regular stacks arise naturally for partial CT and z

AB - Charge transfer (CT) stabilization in linear stacks D+A-D+A- of -electron donors (D) and acceptors (A) involve spin-dependent configuration interactions that are treated exactly in rings of N=4, 6, 8, 10 sites, and extrapolated to N, by adapting valence-bond techniques to electron-hole excitations. The ground state CT (z) and the magnetic gap Em(z)2|t| to the lowest triplet are computed for arbitrary z=2|t|, where -2 is the energy for DAD+A-, -|t|=D+A-|H|DA is the Mulliken CT integral, and D2+, A2- sites are excluded. The spin degeneracy of A- and D+ ion radicals is treated exactly. Instead of the discontinuous change from =0 to =1 in the limit |t|0, finite overlap gives a continuous (z) and (zc)=0.680.01 at the neutral-ionic interface zc=0.530.01. The magnetic gap Em is finite for zzc, where there is a diamagnetic to paramagnetic transition and the ground state switches from k=0 to k= symmetry. Collective effects due to long-range three-dimensional Coulomb interactions are included in a Hartree approximation and produce a first-order transition, with discontinuous (z), when the critical value m2|t|=1.40.1 of the Madelung stabilization m of a dimer is exceeded. The puzzling magnetic gaps in paramagnetic organic CT salts with mixed regular stacks arise naturally for partial CT and z

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U2 - 10.1103/PhysRevB.18.1991

DO - 10.1103/PhysRevB.18.1991

M3 - Article

AN - SCOPUS:0000730183

VL - 18

SP - 1991

EP - 2003

JO - Physical Review B-Condensed Matter

JF - Physical Review B-Condensed Matter

SN - 0163-1829

IS - 4

ER -