When chopped light impinges on a solid in an enclosed cell, an acoustic signal is produced within the cell. This effect is the basis of a new spectroscopic technique for the study of solid and semisolid matter. A quantitative derivation is presented for the acoustic signal in a photoacoustic cell in terms of the optical, thermal, and geometric parameters of the system. The theory predicts the dependence of the signal on the absorption coefficient of the solid, thereby giving a theoretical foundation for the technique of photoacoustic spectroscopy. In particular, the theory accounts for the experimental observation that with this technique optical absorption spectra can be obtained for materials that are optically opaque.

Theory of the photoacoustic effect with solids

The theory of the photoacoustic effect is extended to include the contribution of mechanical vibration of the sample. Coupled equations for thermal and acoustic waves are solved in both sample and gas. It is shown that the pressure signal in the gas may be significantly affected by acoustic coupling in the sample, and experimental confirmation of this extended theory is given. The results of the fully coupled treatment are shown to be accurately reproduced by an extension of the Rosencwaig piston model: the pistonlike motion of the gas boundary layer adjoining the sample is superimposed on the mechanical vibration of the sample surface to give a composite piston displacement which then produces the pressure signal in the gas. The composite‐piston model provides relatively simple algebraic results applicable to many cases of physical interest.

Generalized theory of the photoacoustic effect

Photoacoustic spectroscopy. New tool for investigation of solids

—The use of photoacoustic spectroscopy in the study of photoactive samples (photochemical, luminescent, photovoltaic) is considered. After a short explanation of the parameters important in this technique and ways of measuring them, photochemical processes are considered in detail. Relations are derived for the determination of the energy stored in photochemical products and the quantum yield for the photochemical processes.



One- and two-step photochemical processes are treated in detail and the dependence of the photo-acoustically detected products on modulation frequency is considered, showing the possibility of separating reaction steps according to their rate constants. Particular attention is given to the photosynthetic process and the potential of this method for determination of energy conversion efficiencies of the different stages of photosynthesis is demonstrated. Also the use of the technique in the study of photovoltaic processes is outlined.

Photoacoustic spectroscopy and radiant energy conversion: theory of the effect with special emphasis on photosynthesis

Chopped light impinging on a solid sample in an enclosed cell produces an acoustic signal within the cell. A derivation for the acoustic pressure supports the experimental observation that optical ...

Stan S. Hall

Papers

Thin-layer chromatography and photoacoustic spectrometry