Ab Initio SCF MO Calculation of Ionisation Energies and Charge Distributions of TCNQ and Its Mono- and Divalent Anions

Ab initio SCF MO calculations using a contracted double zeta basis set of 168 gaussian type functions were performed on TCNQ+, TCNQ, TCNQ- and TCNQ2-. The ionisation potentials obtained from total energy differences are generally 0.25-0.50 eV higher than the corresponding negative orbital energies from the TCNQ calculation and in satisfactory agreement with experimental results. The energy of the disproportionation reaction 2TCNQ- → TCNQ + TCNQ2- is calculated to be 4.62 eV. The charge distributions as measured by the gross atomic populations generally deviate from those obtained in earlier π-electron calculations as a consequence of taking the σ-electron distribution into account. The atomic charges are in good agreement with the limited experimental data available.