Chiral molecules interact and react differently with other chiral objects, depending on their handedness. Therefore, it is essential to understand and ultimately control the evolution of molecular chirality during chemical reactions. Although highly sophisticated techniques for the controlled synthesis of chiral molecules have been developed, the observation of chirality on the natural femtosecond time scale of a chemical reaction has so far remained out of reach for isolated molecules.Here, we demonstrate a general experimental technique, based on high-harmonic generation in tailored laser fields, and apply it to probe the time evolution of molecular chirality during the photodissociation of 2-iodobutane. These measurements show a change in sign and a pronounced increase in the magnitude of the chiral response over the first 100 fs, followed by its decay within less than 500 fs, revealing the photodissociation to achiral products. The observed time evolution is explained in terms of the variation of the electric and magnetic transition-dipole moments between the lowest electronic states of the cation as a function of the reaction coordinate. These results open the path to investigations of the chirality of molecular reaction pathways, light-induced chirality in chemical processes and the control of molecular chirality through tailored laser pulses. SIGNIFICANCE STATEMENTChiral molecules interact and react differently, depending on their handedness (left vs. right). This chiral recognition is the basic principle governing most biomolecular interactions, such as the activity of drugs or our perception of scents. Inspite of this fundamental importance, a real-time (femtosecond) observation of chirality during a chemical reaction has remained out of reach for isolated molecules. In the present work, we report this fundamental breakthrough with a seemingly unlikely technique: high-harmonic generation (HHG) in tailored intense near-infrared laser fields. Combining the powerful transient-grating technique with HHG in counter-rotating circularly-polarized laser fields, we follow the temporal evolution of molecular chirality during a chemical reaction from the unexcited electronic ground state through the transition-state region to the final achiral products.

Abstract. Homonuclear decoupling sequences in solid-state nuclear magnetic resonance (NMR) under magic-angle spinning (MAS) show experimentally significantly larger residual line width than expected from Floquet theory to second order. We present an in-depth theoretical and experimental analysis of the origin of the residual line width under decoupling based on frequency-switched Lee–Goldburg (FSLG) sequences. We analyze the effect of experimental pulse-shape errors (e.g., pulse transients and B1-field inhomogeneities) and use a Floquet-theory-based description of higher-order error terms that arise from the interference between the MAS rotation and the pulse sequence. It is shown that the magnitude of the third-order auto term of a single homo- or heteronuclear coupled spin pair is important and leads to significant line broadening under FSLG decoupling. Furthermore, we show the dependence of these third-order error terms on the angle of the effective field with the B0 field. An analysis of second-order cross terms is presented that shows that the influence of three-spin terms is small since they are averaged by the pulse sequence. The importance of the inhomogeneity of the radio-frequency (rf) field is discussed and shown to be the main source of residual line broadening while pulse transients do not seem to play an important role. Experimentally, the influence of the combination of these error terms is shown by using restricted samples and pulse-transient compensation. The results show that all terms are additive but the major contribution to the residual line width comes from the rf-field inhomogeneity for the standard implementation of FSLG sequences, which is significant even for samples with a restricted volume.

Understanding the chirality of molecular reaction pathways is essential for a broad range of fundamental and applied sciences. However, the current ability to probe chirality on the time scale of primary processes underlying chemical reactions remains very limited. Here, we demonstrate time-resolved photoelectron circular dichroism (TRPECD) with ultrashort circularly polarized vacuum-ultraviolet (VUV) pulses from a tabletop source. We demonstrate the capabilities of VUV-TRPECD by resolving the chirality changes in time during the photodissociation of atomic iodine from two chiral molecules. We identify several general key features of TRPECD, which include the ability to probe dynamical chirality along the complete photochemical reaction path, the sensitivity to the local chirality of the evolving scattering potential, and the influence of electron scattering off dissociating photofragments. Our results are interpreted by comparison with high-level ab-initio calculations of transient PECDs from molecular photoionization calculations. Our experimental and theoretical techniques define a general approach to femtochirality.

<p><strong>Abstract.</strong> Homonuclear decoupling sequences in solid-state NMR under magic-angle spinning (MAS) show experimentally significantly larger residual linewidth than expected from Floquet theory to second order. We present an in-depth theoretical and experimental analysis of the origin of the residual linewidth in frequency-switched Lee-Goldburg (FSLG) based decoupling sequences. We analyze the effect of experimental pulse-shape errors (<i>e.g.</i> pulse transients and <i>B</i><sub>1</sub>-field inhomogeneities) and use a Floquet-theory based description of higher-order error terms that arise from the interference between the MAS rotation and the pulse sequence. It is shown that the magnitude of the third-order auto term of a single homo- or heteronuclear coupled spin pair is important and leads to significant line broadening under FSLG decoupling. Furthermore, we show the dependence of these third-order error terms on the angle of the effective field with the <i>B</i><sub>0</sub> field. An analysis of second-order cross terms is presented that shows that the influence of three-spin terms is small since they are averaged by the pulse sequence. The importance of the static rf-field inhomogeneity is discussed and shown to be the main source of residual line broadening while pulse transients do not seem to play an important role. Experimentally, the influence of the combination of these error terms is shown by using restricted samples and pulse-transient compensation. The results show that all terms are additive but the major contribution to the residual linewidth comes from the rf-field inhomogeneity for the standard implementation of FSLG sequences, which is significant even for samples with a restricted volume.</p>

' &,, but it can be seen in their spatial dependence that they are minimized around the magic-angle except the),) term. ',' = 1 G ' () &,' , sin() ' sin(2) '