Optimized ground-state geometries of three exemplary dinitrile compounds: N2C8H12 (top), N2C8H6 (middle), and N2C8 (bottom).
Computed N1s single ionization potentials and their constituting parts (see Eq. (1)) as functions of the molecular length and the carbon bridge type in the bridged dinitriles. n refers to the number of the chain units. These units are shown at the left lower corner of panel (c). Filled circles correspond to the ab initio results. Dashed lines are fitting functions defined by the polynomials .
Computed tsDIP(N1s, N1s) as a function of the molecular length and the carbon bridge type in the bridged dinitriles. n refers to the number of chain units. Filled circles correspond to the ab initio data. Dashed lines are fitting functions defined by the polynomials .
Calculated interatomic relaxation (IR, color circles) and correlation (IC, color squares) energies as functions of the molecular length and the carbon bridge type in the bridged dinitriles. The two grey symbols refer to the unbridged dinitrile (cyanogen). The values of the IC energies are joined by solid lines. Dashed lines are fitting functions for the IR energies defined by the polynomials .
The IR energy as calculated using Eq. (19) (open circles). The solid line is a fitting function of the type a(ln N) b /N c . The IR energy is given in η = −1/(βd 2) units, where β is the resonance integral and d is the distance between neighboring atoms.
Generalized Wagner plots for the dinitriles bridged by different carbon chains drawn as described in Sec. III C. The core level IP of a nitrogen atom is plotted on the horizontal axis. The core level IP of the same nitrogen atom in the presence of a core vacancy on the other nitrogen atom is plotted on the vertical axis. The core holes repulsion energies are subtracted from the latter IPs. Ab initio values (filled circles) are joined by straight solid lines to guide the eye. The diagonal lines with slope +1 corresponds to the levels of constant IR energies.
Selected bondlengths and total lengths (in Å), the Mulliken charges on the terminal nitrogen atoms (Q, in e) and the HOMO-LUMO gaps (H-L, in eV) in the bridged dinitrile molecules studied.
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