A theoretical study on the mechanism of charge transfer state formation of 4-(N,N-dimethylamino)benzonitrile in an aqueous solution

Abstract

The mechanism of charge transfer (CT) state formation of excited state 4‐(N,N‐dimethylamino)benzonitrile (DMABN) in an aqueous solution has been studied theoretically. Ab initio configuration interaction (CI) calculations were carried out for the potential energy surfaces of ground and excited state DMABN. The potential surface of second excited S₂ state was represented by a superposition of three diabatic states, one is of the ion pair type and the other two of the neutral ones, to facilitate the calculations in a polar solution. The intermolecular pair potentials between DMABN and H₂O were developed with the aid of electron distributions in DMABN obtained from ab initio calculations. These potential functions were applied to determine the geometries of DMABN–H₂O complex and the results were compared with the available experimental data. Monte Carlo simulation calculations were further performed for the aqueous solution of DMABN. The potentials of mean force for the torsional angle of dimethylamino group revealed that the S₂ state potential profile is remarkably altered due to the solvation and the twisted intramolecular CT state becomes a stable point on the surface while this point corresponds to the top of potential barrier in the gas phase. The origin of broad emission band at a longer wavelength region observed in the experiments were discussed on the basis of present calculations. In order to elucidate the mechanism of CT state formation, the reaction free energy surfaces were constructed as the function of solvation coordinate and amino torsional angle. The results obtained here were that: (a) the shape of free energy curve of S₂ state is far from a parabolic form along the solvation coordinate while the S₁ state curve is nearly parabolic; and (b) the torsional coordinate is required to undergo a deformation to reach the transition state region of CT state formation reaction.