Selecting Initial Conditions for Trajectory-Based Nonadiabatic Simulations.

ConspectusPhotochemical reactions have always been the source of a great deal of mystery. While classified as a type of chemical reaction, no doubts are allowed that the general tenets of ground-state chemistry do not directly apply to photochemical reactions. For a typical chemical reaction, understanding the critical points of the ground-state potential (free) energy surface and embedding them in a thermodynamics framework is often enough to infer reaction yields or characteristic time scales.

Sensitivity Analysis in Photodynamics: How Does the Electronic Structure Control -Stilbene Photodynamics?

The techniques of computational photodynamics are increasingly employed to unravel reaction mechanisms and interpret experiments. However, misinterpretations in nonadiabatic dynamics caused by inaccurate underlying potentials are often difficult to foresee. This work focuses on revealing the systematic errors in the nonadiabatic simulations due to the underlying potentials and suggests a thrifty approach to evaluate the sensitivity of the simulations to the potential.

From boom to bloom: synthesis of diazidodifluoromethane, its stability and applicability in the 'click' reaction.

Diazidodifluoromethane was prepared from dibromodifluoromethane, sodium azide and an alkanethiolate initiator. It represents the first example of a diazidomethane that is stable enough to be used in synthesis. The stability of (poly)azidomethanes was explored with calculations.

From Gas to Solution: The Changing Neutral Structure of Proline upon Solvation.

Liquid-jet photoelectron spectroscopy (LJ-PES) and electronic-structure theory were employed to investigate the chemical and structural properties of the amino acid l-proline in aqueous solution for its three ionized states (protonated, zwitterionic, and deprotonated). This is the first PES study of this amino acid in its biologically relevant environment. Proline's structure in the aqueous phase under neutral conditions is zwitterionic, distinctly different from the nonionic neutral form in the gas phase.

Attosecond formation of charge-transfer-to-solvent states of aqueous ions probed using the core-hole-clock technique.

Charge transfer between molecules lies at the heart of many chemical processes. Here, we focus on the ultrafast electron dynamics associated with the formation of charge-transfer-to-solvent (CTTS) states following X-ray absorption in aqueous solutions of Na, Mg, and Al ions. To explore the formation of such states in the aqueous phase, liquid-jet photoemission spectroscopy is employed.