화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.104, No.32, 7452-7463, 2000
Mechanisms of solvent shifts, pressure shifts, and inhomogeneous broadening of the optical spectra of dyes in liquids and low-temperature glasses
Optical absorption spectra were measured in liquid solutions at ambient temperature for comparatively nonpolar chromophores: polymethine dyes, polycyclic hydrocarbons, and tetrapyrrolic compounds. The analysis of solvent shifts of band maxima as a function of polarity, polarizability, and hydrogen bonding properties of the medium allows one to distinguish several solvent shift mechanisms. Solvent polarizability dependent red shifts are assigned to dispersive interaction. Hypsochromism in the spectra of open chain cyanine dyes and s-tetrazine in polar media may be understood in terms of a multipolar reaction field. Blue shifts of the visible bands of anionic dyes, resorufin, and resazurin occur in alcohols due to the hydrogen bonding with the solvent. Both the polar solvation and the H-bonding with water in the center of tetrapyrrolic macrocycle is responsible for the blue shifts of the S-1-S-0 band in porphyrins. inhomogeneous bandwidths were measured in ethanol glass at 6 K. The reason of inhomogeneous broadening is the spread of microscopic solvent shifts in the disordered matrix that can have the same mechanisms as the macroscopic shifts of band maxima. Alternatively, other broadening mechanisms such as the linear Stark effect in the solvent cavity field do not shift the spectral band as a whole. Further, spectral holes were burned in the inhomogeneous S-1 <-- S-0 absorption bands in glassy ethanol and the pressure shift coefficients of the holes d nu/dP were determined using gaseous He as pressure transmitter. d nu/dP shows a linear dependence on hole burning wavenumber that can be extrapolated to the frequency nu(0(P)) where pressure shift disappears. The nu(0(P)) values deviate significantly from the actual 0-0 origins of nonsolvated chromophores. The slope of the dependence of d nu/dP on hole frequency generally differs from the value of 2 beta(T) (beta(T) is the isothermal compressibility of the matrix), predicted for the dispersive solvent shift. The slopes steeper than 2 beta(T) were assigned to short-range repulsive forces. The long-range electrostatic interactions must lead to the slope values less than beta(T).