According to experimental data available for the complex refractive index of particular dielectrics, a dielectric spectrum formula is proposed by the least square fitting technique combined with selected natural frequencies. From the dielectric spectrum formula, the spectra of optical and dielectric constants can be obtained in the whole frequency region. Three dielectrics, water, ethanol, and toluene, are taken as examples. In the region where the ex- perimental data are available, the spectra of the optical constants calculated by the formula are in good agreement with the real refractive spectrum obtained by Kramers-Kronig （K-K） transform and the experimental imaginary refractive spectrum. In the region where no ex- perimental data are available, the extrapolation of our formula can make predictions. The merits of the present treatment are that we are able to get the uniform spectrum formula, without splitting into different frequency sections, and the analytical form of the dielectric spectra will be useful in the theoretical description of solvation dynamics.
Based on the constrained equilibrium state theory,the nonequilibrium solvation energy is derived in the framework of the continuum model.The formula for spectral shift and vertical ionization energy are deduced for a single sphere cavity with the point charge assumption.The new model is adopted to investigate the vertical ionization for halogen atomic and molecular anions X(X = Cl,Br,I,Cl2,Br2,I2) in aqueous solution.According to the calculation using the CCSD-t/aug-cc-pVQZ method in vacuum,our final estimated vertical ionization energies in solution are very close to the experimental observations,while the traditional nonequilibrium solvation theory overestimates these vertical ionization energies.
CHENG XueMin,ZHU Quan,WANG XingJian,LI YunKui & LI XiangYuan College of Chemical Engineering,Sichuan University,Chengdu 610065,China
