A new four-wave-mixing technique with evanescent optical fields generated by total internal reflection at a liquid-liquid interface is described. Several applications of this method to measure thermoacoustic and dynamic properties near liquid-liquid interfaces are presented.

Transient grating experiments performed with evanescent fields resulting from total internal reflection at an interface between a polar absorbing solution and an apolar transparent solvent are described. The time evolution of the diffracted intensity was monitored from picosecond to millisecond time scales. The diffracted signal originates essentially from two density phase gratings:  one in the absorbing phase induced by thermal expansion and one in the transparent solvent due to electrostriction. A few nanoseconds after excitation, the latter grating is replaced by a thermal grating due to thermal diffusion from the absorbing phase. The speed of sound and the acoustic attenuation measured near the interface are found to be essentially the same as in the bulk solutions. However, after addition of a surfactant in the polar phase, the speed of sound near the interface differs substantially from that in the bulk with the same surfactant concentration. This effect is interpreted in terms of adsorption at the liquid/liquid interface. Other phenomena, which are not observed in bulk experiments, such as acoustic echoes and a fast oscillation of the signal intensity, are also described.

The dynamics of exciplex and radical ion formation was studied in donor–acceptor systems with G ^* _et > –0.1 eV. It was shown that the quenching of excited singlet states of aromatic molecules by electron donors in polar solvents led to the formation of radical ions via exciplex dissociation resulting to complete charge separation. Intersystem crossing and internal conversion into the ground state (back electron transfer) compete with this process. The quantum yields and the rate constants of the radical ion formation were measured.

A transient grating setup with evanescent wave probing has been developed to investigate ultrafast processes at liquid–liquid interfaces. In order to evaluate the selectivity of this method to the interface, the speed of sound in the low refractive index medium has been measured as a function of the penetration depth of the probe pulse. Our preliminary results indicate an increase of the speed of sound in methanol with decreasing the probe depth from 100 to 70 nm. However, no correlation was found in acetonitrile in the same range. Modifications of the experiment for improving the selectivity to the interface are proposed.

The excited-state dynamics of the radical cations of perylene (PE^•+), tetracene (TE^•+), and thianthrene (TH^•+), as well as the radical anions of anthraquinone (AQ^•-) and tetracenequinone (TQ^•-), formed by γ irradiation in low-temperature matrices (PE^•+, TH^•+, AQ^•-, and TQ^•-) or by oxidation in sulfuric acid (PE^•+, TE^•+, and TH^•+) have been investigated using ultrafast pump−probe spectroscopy. The longest ground-state recovery time measured was 100 ps. The excited-state lifetime of PE^•+ is substantially longer in low-temperature matrices than in H₂SO₄, where the effects of perdeuteration and of temperature on the ground-state recovery dynamics indicate that internal conversion is not the major decay channel of PE^•+*. The data suggest that both PE^•+* and TE^•+* decay mainly through an intermolecular quenching process, most probably a reversible charge transfer reaction. Contrarily to AQ^•-*, TQ^•-* exhibits an emission in the visible which, according to theoretical calculations, occurs from an upper excited state.

A study of the dynamics of electronic energy transfer (EET) in arrays containing three, four, and six tetraphenylporphine units connected with phenylethynyl spacers is reported. For arrays containing the same chromophores, the EET rate constant was determined from the reorientational dynamics of the transition dipole using the crossed grating technique. EET time constants ranging from 150 ps up to 33 ns were measured, depending on the distance between the chromophores and on the metal ion complexed in the porphyrins. For the trimeric planar arrays, the interchromophoric distance varies by a factor of 2, while the ratio of the through space to through bond distances is constant. By comparing the measured EET rate constants with those calculated using Förster theory, the contributions of the Coulombic, through space, mechanism and of the exchange, through bond, mechanism could be estimated. For the arrays with the shortest spacer (through space distance of 23 Å), EET occurs through both exchange and Coulombic interactions with a ratio of about 3:1. This ratio increases up to about 10 as the distance is increased to 34.5 Å. At 46.5 Å, the ratio decreases and it appears that the Coulombic interaction becomes the dominant mechanism at longer distances. In the tetrahedral compound, the presence of a central saturated carbon strongly alters the electronic conducting properties of the spacer and makes the exchange mechanism inoperative.

The deactivation of the S₁(Ï€,Ï€^*) excited state of nickel tetraphenylporphine has been investigated using various transient grating techniques. By measuring the density changes of the sample occurring during this process, the excited state, that is responsible for the ground state recovery time of 250 ps, was determined to lie 1.18±0.13 eV above the ground state. This value suggests that this state is the¹(d,d) state.