Cubane and cubanoid: Structural, optoelectronic and thermodynamic properties from DFT and TD-DFT method.

In this paper, we report structural, electronic and optical properties of cubane (C8H8) and cubanoids (cubane-like molecules) using Density Functional Theory (DFT). The cubanoids are cubanes for which Carbon atoms have been substituted by Nitrogen (N), Phosphorus (P), Boron (B), Silicon (Si), Arsenic (As), Antimony (Sb) or Bismuth (Bi) atoms. These molecules presented exceptional stability with several different symmetry point groups, being the majority Td. All calculated vibrational frequencies are positive for any studied molecules indicating that all these structures are in a stable state. The HOMO-LUMO gaps and DOS were calculated converged towards to values between 1.87 eV and 5.61 eV, actually showing promising electronic properties (Just for comparison, the cubane energy gap is 7.50 eV). The optical absorptions were also calculated for the cubanoid structure using the Time-Dependent Density Functional Theory (TD-DFT). Their dependence on the wavelength is analyzed, where five of theses structures absorb on the visible region. Finally, the extrapolation of thermodynamic properties indicates that these cubanoid could be potentially synthesized spontaneously, where four structures, the synthesis would occur for temperatures below 400 K, while for Si4Bi4H4 structure, the synthesis would occur at room temperature.