Charge localization and Jahn–Teller distortions in the benzene dimer cation

Piotr A. Pieniazek; Stephen E. Bradforth; Anna I. Krylov

doi:10.1063/1.2969107

Charge localization and Jahn–Teller distortions in the benzene dimer cation

The Journal of Chemical Physics ◽

10.1063/1.2969107 ◽

2008 ◽

Vol 129 (7) ◽

pp. 074104 ◽

Cited By ~ 71

Author(s):

Piotr A. Pieniazek ◽

Stephen E. Bradforth ◽

Anna I. Krylov

Keyword(s):

Charge Localization ◽

Benzene Dimer ◽

Jahn Teller

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Charge Localization in Stacked Radical Cation DNA Base Pairs and the Benzene Dimer Studied by Self-Interaction Corrected Density-Functional Theory

The Journal of Physical Chemistry A ◽

10.1021/jp063080n ◽

2007 ◽

Vol 111 (1) ◽

pp. 105-112 ◽

Cited By ~ 35

Author(s):

Yves A. Mantz ◽

Francesco Luigi Gervasio ◽

Teodoro Laino ◽

Michele Parrinello

Keyword(s):

Density Functional Theory ◽

Radical Cation ◽

Density Functional ◽

Base Pairs ◽

Functional Theory ◽

Charge Localization ◽

Dna Base ◽

Dna Base Pairs ◽

Benzene Dimer

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Bare Molecular Anions of Unsaturated Hydrocarbons: Density Functional Charge and Spin Distributions Based on Their Single Crystal Structures

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19981245 ◽

1998 ◽

Vol 63 (8) ◽

pp. 1245-1263 ◽

Cited By ~ 3

Author(s):

Zdeněk Havlas ◽

Hans Bock

Keyword(s):

Alkali Metal ◽

Conformational Changes ◽

Density Functional ◽

Structural Data ◽

Radical Anions ◽

Spin Distribution ◽

Open Chain ◽

Charge Localization ◽

Jahn Teller ◽

Spin Populations

Bare π-hydrocarbon radical anions M•, dianions M− as well as even a radical trianion M• can be crystallized as alkali metal salts, [M(•)−n][Me+solv]n if the solvent-shared contact ion multiples, [M(•)−n..(Me+)n]solv, present in aprotic solution after the reduction at an alkali metal mirror can be separated by advantageous cation solvation. Altogether 22 π-hydrocarbon anions M(•)−n comprising polycyclic cata- as well as peri-annelated six-membered ring compounds, polyphenyls, those with nonalternant polycyclic skeletal topology, open chain and organosilicon derivatives have been characterized by low-temperature X-ray crystallographic analyses. Based on the structural data determined, their charge and spin populations have been approximated by density functional calculations including natural bond orbital analyses (DFT/NBO). Although in general the total (σ + π) charges at individual C centers of the hydrocarbon skeletons cannot be correlated neither with the structural data nor with the spin distribution, numerous interesting details as well as some useful rules are provided. They concern, for instance, central C-C bond elongation and peripheral C-C bond shortening, preferred charge localization patterns, effects of conformational changes in the π-radical anions crystallized or Jahn-Teller distortions of formally degenerate molecular radical anion states.

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