Distinctive Photomechanical Shape Change of p-Phenylenediacrylic Acid Dimethyl Ester Single Crystals Induced by a Spatially Heterogeneous Photoreaction.

Understanding photoreaction dynamics in crystals is important for predicting the dynamic property changes accompanying these photoreactions. In this work, we investigate the photoreaction dynamics of p-phenylenediacrylic acid dimethyl ester (p-PDAMe) in single crystals that show reaction front propagation, in which the photoreaction proceeds heterogeneously from the edge to the center of the crystal. Moreover, we find that p-PDAMe single crystals exhibit a distinctive crystal shape change from a parallelogram to a distorted shape resembling a fluttering flag, then to a rectangle as the photoreaction proceeds.

The interplay of density functional selection and crystal structure for accurate NMR chemical shift predictions.

chemical shift prediction plays a central role in nuclear magnetic resonance (NMR) crystallography, and the accuracy with which chemical shifts can be predicted relative to experiment impacts the confidence with which structures can be assigned. For organic crystals, periodic density functional theory calculations with the gauge-including projector augmented wave (GIPAW) approximation and the PBE functional are widely used at present. Many previous studies have examined how using more advanced density functionals can increase the accuracy of predicted chemical shifts relative to experiment, but nearly all of those studies employed crystal structures that were optimized with generalized-gradient approximation (GGA) functionals.