Two-photon Absorption - TPA Compounds

TPA Compounds

To some extent, linear and 2-photon absorption strengths are linked. Therefore, the first compounds to be studied (and many that are still studied and used in e.g. 2-photon microscopy) were standard dyes. In particular, laser dyes were used, since these have good photostability characteristics. However, these dyes tend to have 2-photon cross-sections of the order of 0.1-10 GM, much less than is required to allow simple experiments.

It was not until the 1990s that rational design principles for the construction of two-photon-absorbing molecules began to be developed, in response to a need from imaging and data storage technologies, and aided by the rapid increases in computer power that allowed quantum calculations to be made. The accurate quantum mechanical analysis of two-photon absorbance is orders of magnitude more computationally intensive than that of one-photon absorbance, requiring highly correlated calculations at very high levels of theory.

The most important features of strongly TPA molecules were found to be a long conjugation system (analogous to a large antenna) and substitution by strong donor and acceptor groups (which can be thought of as inducing nonlinearity in the system and increasing the potential for charge-transfer). Therefore, many push-pull olefins exhibit high TPA transitions, up to several thousand GM. It is also found that compounds with a real intermediate energy level close to the "virtual" energy level can have large 2-photon cross-sections as a result of resonance enhancement.

Compounds with interesting TPA properties also include various porphyrin derivatives, conjugated polymers and even dendrimers. In one study a diradical resonance contribution for the compound depicted below was also linked to efficient TPA. The TPA wavelength for this compound is 1425 nanometer with observed TPA cross section of 424 GM.