Aromaticity on the fly: cyclic transition state stabilization at finite temperature.

We study the transition state of pericyclic reactions at elevated temperature with unbiased ab initio molecular dynamics. We find that the transition state of the intramolecular rearrangements for barbaralane and bullvalene remains aromatic at high temperature despite the significant thermal atomic motions. Structural, magnetic, and electronic properties of the dynamical transition state show the concertedness and aromatic character. Free-energy calculations also support the validity of the transition state theory for the present rearrangement reactions. The calculations demonstrate that cyclic delocalization represents a strong force to synchronize the thermal atomic motions even at high temperatures.

Nucleon 3PF2 Superfluid Pairing Gap in Asymmetry Nuclear Matter

The 3PF2 superfluidity of neutron and proton is investigated in isospin-asymmetric nuclear matter within the Brueckner–Hartree–Fock approach and the BCS theory by adopting the Argonne V14 and the Argonne V18 nucleon-nucleon interactions. We find that pairing gaps in the 3PF2 channel predicted by adopting the AV14 interaction are much larger than those by the AV18 interaction. As the isospin-asymmetry increases, the neutron 3PF2 superfluidity is found to increase rapidly, whereas the proton one turns out to decrease and may even vanish at high enough asymmetries.As a consequence, the neutron 3PF2 superfluidity is much stronger than the proton one at high asymmetries and it predominates over the proton one in dense neutron-rich matter.