The 2-carbamoylnaphthol with active point substituted.
ⅰ) Due to the introduction of halogen atom into the carbon atom of 2-carbamoylnaphthol's active point,
the energy level of this 2-equivalnt 2-carbamoylnaphthol's (Next)HOMO(E*nr) goes down the less than the appropriate range to make the coupling rate slow.
(When a halogen atom is introduced into the carbon at the coupler's active point,
it is necessary to concider not only the energy level of HOMO but also the energy level of NextHOMO.)
It correspond to the case of k'>>k, mentioned in "The first reaction kinetics in the world with regard to indoaniline dye forming (4)",
since the indoaniline dye forming rate from this 2-equivalnt 2-carbamoylnaphthol goes down, the density of dye is the less than the enough one.
ⅱ)Due to the introduction of substituent through the oxygen atom into the carbon atom of 2-carbamoylnaphthol's active point,
the energy level of this 2-equivalnt 2-carbamoylnaphthol's HOMO(E*nr) goes up within the appropriate range.
It does not impair the rate of couplling reaction but it does not reach to a point that acceralate the one, due to the incapability to avoid decrease the molecular orbital coefficient of carbon atom on this 2-equivalnt 2-carbamoylnaphthol's active point.
Still, the magical world goes around!
⊿Etotal=ーqr・qs ／ Rrs ＋2(Cmｒr・ Cnｓs・⊿β)² ／(E*nrーE*ms)
(the second term) (the third term) (the first term is omitted)
(coulomb term) (electron transfer interaction term)
where
E*nr is the energy level of the coupler anion's HOMO,
E*ms is the energy level of quinonediimine's LUMO,
Cmrr is the molecular orbital coefficient of carbon atom on the coupler's(HOMO's) active point ,
Cnss is the molecular orbital coefficient of nitrogen atom on the quinonediimine's(LUMO's) reaction point ,
Δβ is the stabilization energy due to the formation of CN bond.
It's equivalent to the amount of change in the resonance integral.
