These events happen very quickly compared to typical molecular relaxation times, so the carbocation is usually created in the same conformation and electronic configuration as the original neutral molecule. For example, decay of tritiated methane, (R = R ' = R " = H) produces the carbenium ion in a tetrahedral conformation, with one of the orbitals having a single unpaired electron and the other three forming a trigonal pyramid. The ion then relaxes to its more favorable trigonal planar form, with release of about 30 kcal/mol of energy—that goes into vibrations and rotation of the ion. In a condensed phase, the carbocation can also gain an electron from surrounding molecules, thus becoming an electrically neutral radical. For example, in crystalline naphthalene, a molecule with tritium substituted for hydrogen in the 1 (or 2) position will be turned by decay into a cation with a positive charge at that position. That charge will however be quickly neutralized by an electron transported through the lattice, turning the molecule into the 1-naphthyl (or 2-naphthyl) radical; which are stable, trapped in the solid, below 170 K .
These events happen very quickly compared to typical molecular relaxation times, so the carbocation is usually created in the same conformation and electronic configuration as the original neutral molecule. For example, decay of tritiated methane, (R = R ′ = R ″ = H) produces the carbenium ion in a tetrahedral conformation, with one of the orbitals having a single unpaired electron and the other three forming a trigonal pyramid. The ion then relaxes to its more favorable trigonal planar form, with release of about 30 kcal/mol of energy—that goes into vibrations and rotation of the ion. In a condensed phase, the carbocation can also gain an electron from surrounding molecules, thus becoming an electrically neutral radical. For example, in crystalline naphthalene, a molecule with tritium substituted for hydrogen in the 1 (or 2) position will be turned by decay into a cation with a positive charge at that position. That charge will however be quickly neutralized by an electron transported through the lattice, turning the molecule into the 1-naphthyl (or 2-naphthyl) radical; which are stable, trapped in the solid, below .
R
'
′
R
"
″
D
170 K