The unexpected effect of aqueous ion pairs on the forbidden n →π* transition in nitrate.

Aqueous nitrate is ubiquitous in the environment, found for example in stratospheric clouds, tropospheric particulate matter, rain and snow, fertilized fields, rivers and the ocean. Its photolysis is initiated by absorption into the strongly forbidden n →π* transition. Photolysis reactivates deposited nitrate, releasing nitrogen oxides, and UV light is commonly used to break down nitrate pollution. The transition is doubly forbidden unless its symmetry is broken, giving a powerful means of probing the interactions of nitrate with its environment and of using experiment to validate the results of theory. In this study we demonstrate the remarkably different effects of the addition of a series of mono- and di-valent metal chlorides on the nitrate UV transition. While they all shift the transition to shorter wavelengths, the shift changes significantly from one to another. For the monovalent series Li