We calculate the maximum power conversion efficiency for conversion of solar radiation to electrical power or to a flux of chemical free energy for the case of hydrogen production from water photoelectrolysis. We consider several types of ideal absorbers where absorption of one photon can produce more than one electron-hole pair that are based on semiconductor quantum dots with efficient multiple exciton generation (MEG) or molecules that undergo efficient singlet fission (SF). Using a detailed balance model with 1 sun AM1.5G illumination, we find that for single gap photovoltaic (PV) devices the maximum efficiency increases from 33.7% for cells with no carrier multiplication to 44.4% for cells with carrier multiplication. We also find that the maximum efficiency of an ideal two gap tandem PV device increases from 45.7% to 47.7% when carrier multiplication absorbers are used in the top and bottom cells. For an ideal water electrolysis two gap tandem device, the maximum conversion efficiency is 46.0% using a SF top cell and a MEG bottom cell versus 40.0% for top and bottom cell absorbers with no carrier multiplication. We also consider absorbers with less than ideal MEG quantum yields as are observed experimentally.

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The ASTM G-173–3 Reference Solar Spectra can be found at http://rredc. nrel.gov/solar/spectra/am1.5/.
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