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Owing to the absence of oxygen and ozone in the Archean atmosphere, ultraviolet light has been considered as one of the key sources of energy driving prebiotic chemistry and abiotic selection of biomolecular building blocks. Consequently, various experimental and theoretical efforts have been made to study the photostability of primary components of biomolecules and selective UV-assisted chemical routes to these compounds. In this book chapter, I summarize the most important advances in this field from the perspective of theoretical chemistry, time-resolved spectroscopy and organic synthesis. I also emphasize the importance of embedding these scenarios in a relevant planetary context. Establishing connections between these different points of view on prebiotic photochemistry allows one to rethink the role of photostability, RNA/DNA self-repair and selective photochemical transformations in the emergence of biomolecular building blocks on Earth.

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