Solvent Triggered Change of the Electron Excitation Route of KI in Supercritical NH3

GERMÁN SCIAINI; ERNESTO MARCECA; ROBERTO FERNÁNDEZ PRINI

JOURNAL OF PHYSICAL CHEMISTRY B

American Chemical Society

Año: 2006 vol. 110 p. 8921 - 8923

1089-5647

The UV-spectroscopic behavior of KI contact ion pairs (CIPs) dissolved in supercritical NH3 was studied combining classical molecular dynamics simulations with electronic structure calculations, and the results show that an abrupt change of the photoexcitation route of KI CIPs occurs at very low solvent densities. Few NH3 solvating molecules are required to hamper the well-known photoinduced intramolecular electron (e-) transfer observed in isolated ion pairs of alkali metal halides in the vapor drawing the e- to solvent cavities leading to a charge-transfer-to-solvent process.3 was studied combining classical molecular dynamics simulations with electronic structure calculations, and the results show that an abrupt change of the photoexcitation route of KI CIPs occurs at very low solvent densities. Few NH3 solvating molecules are required to hamper the well-known photoinduced intramolecular electron (e-) transfer observed in isolated ion pairs of alkali metal halides in the vapor drawing the e- to solvent cavities leading to a charge-transfer-to-solvent process.