Conformer-specific Chemistry Imaged in Real Space and Time

Abstract

Conformational isomers or conformers of molecules play a decisive role in chemistry and biology. However, experimental methods to investigate chemical reaction dynamics are typically not conformer-sensitive. Here, we report on a gas-phase megaelectronvolt ultrafast electron diffraction investigation of α-phellandrene undergoing an electrocyclic ring-opening reaction. We directly image the evolution of a specific set of α-phellandrene conformers into the product isomer predicted by the Woodward-Hoffmann rules in real space and time. Our experimental results are in quantitative agreement with nonadiabatic quantum molecular dynamics simulations, which provide unprecedented detail of how conformation influences time scale and quantum efficiency of photoinduced ring-opening reactions. Due to the prevalence of large numbers of conformers in organic chemistry, our findings impact our general understanding of reaction dynamics in chemistry and biology.

References in corpus (4)

• Imaging the Photochemical Ring-Opening of 1,3-Cyclohexadiene by Ultrafast Electron Diffraction
• Specific chemical reactivities of spatially separated 3-aminophenol conformers with cold Ca${}^{+}$ ions
• Spatially-controlled complex molecules and their applications
• State- and conformer-selected beams of aligned and oriented molecules for ultrafast diffraction studies

Cited by in corpus (8)

• Deciphering the Influence of Ground-State Distributions on the Calculation of Photolysis Observables
• Rehybridization dynamics into the pericyclic minimum of an electrcyclic reaction imaged in real-time
• Monitoring the evolution of relative product populations at early times during a photochemical reaction
• Imaging the photochemical dynamics of cyclobutanone with MeV ultrafast electron diffraction
• Real-Space Inversion and Super-Resolution of Ultrafast Scattering
• Prediction challenge: First principles simulation of the ultrafast electron diffraction spectrum of cyclobutanone
• Simulating Ultrafast Transient Absorption Spectra from First Principles using a Time-Dependent Configuration Interaction Probe
• Ultrafast electron diffractive imaging of the dissociation of pre-excited molecules