Photochemistry and UV/vis spectroscopy of hydrated vanadium cations, V<sup>+</sup>(H<sub>2</sub>O)<sub><i>n</i></sub>, <i>n</i> = 1–41, a model system for photochemical hydrogen evolution
Jakob Heller, Tobias F. Pascher, Dominik Muß, Christian van der Linde, Martin K. Beyer, Milan Ončák
Abstract
. For the smallest clusters, the electronic transitions are modeled using multireference methods with spin-orbit coupling. A large number of quintet and triplet states is accessible, which explains the broad features observed in the experiment. Water loss most likely occurs after a series of intersystem crossings and internal conversions to the electronic ground state or a low-lying quintet state, while hydrogen evolution is favored in low lying triplet states.
Topics & Concepts
Intersystem crossingVanadiumPhotochemistrySpectroscopyChemistryTransition metalPhotodissociationExcited stateInorganic chemistryAtomic physicsPhysicsCatalysisBiochemistrySinglet stateQuantum mechanicsElectrocatalysts for Energy ConversionMetalloenzymes and iron-sulfur proteinsPhotosynthetic Processes and Mechanisms