Active nematic liquid crystals simulated by particle-based mesoscopic methods.

Two Multi-particle collision dynamics algorithms that simulate nematic liquid crystals are generalised to reproduce active behaviour. One of the algorithms is due to Shendruk and Yeomans and is based on particles that carry an orientation vector ordered by a mean-field energy [T. N. Shendruk and J. M. Yeomans, Soft Matter, 2015, 11, 5101]. In the other algorithm, due to Mandal and Mazza, particles possess an order parameter tensor which evolves according to the Qian-Sheng model of nematohydrodynamics [S. Mandal and M. G. Mazza, Phys. Rev. E, 2019, 99, 063319]. For both methods activity is incorporated through a force proportional to the divergence of the local average order parameter tensor. Both implementations produce disclination curves in the nematic fluid that undergo nucleation and self-annihilation dynamics. Topological defects are found to be consistent with those observed in recent experiments of three-dimensional active nematics. Results permit to compare the length-scales over which the different nematic Multi-particle collision dynamics methods operate. The structure and dynamics of the orientation and flow fields agree with those obtained recently in numerical studies of continuum three-dimensional active nematics. Overall, our results open the opportunity to use mesoscopic particle-based approaches to study active liquid crystals in situations such as nonequilibrium states driven by flow or colloidal particles in active anisotropic solvents.

Effect of the nO → π*C═O Interaction on the Conformational Preference of 1,3-Diketones: A Case Study of Riolozatrione Derivatives.

The cyclopropane ring-opening reaction of riolozatrione, a natural product obtained from Jatropha dioica, afforded a 2,2-disubstituted 1,3-cyclohexandione displaying an alkyl methyl ether group at position 5. The conformational analysis of this product showed a high preference for the trans-diaxial conformation in both solution and solid state. Such conformation was possible from the noncovalent intramolecular nX → π*C═O interactions (X = an element having an unshared electron pair), allowing the determination of the interaction energies. Since the nX → π*C═O interactions can be regarded as additive, the energy values ranged from 4.52 to 6.51 kcal mol-1 for each carbonyl group with a strong dependency on the interatomic distances. The rigorous analysis of the electron density in the topological theory of atoms in molecules framework clearly shows that the origin of O-C═O interactions are through the nO → π*C═O electron transfer mechanism. Such interactions are slightly weaker than a canonical hydrogen bond but seemingly stronger than a van der Waals interaction. This interaction must be considered as a stereoelectronic effect due the electronic transfer between the interacting groups, which are limited by their relative stereochemistry and can be represented by a bond-no bond interaction, causing the pyramidalization of the carbonyl, which is the charge acceptor group.

Properties of noncovalent tetraphenylporphine···C60 dyads as studied by different long-range and dispersion-corrected DFT functionals.

The noncovalent dyad of tetraphenylporphine and C60 fullerene (H2TPP···C60) and the tetraphenylporphine dimer (H2TPP···H2TPP) were studied by density functional theory (DFT), using functionals that incorporate empirical dispersion correction (DFT-D), functionals that use a long-range correction (LC) scheme, a hybrid functional (B3LYP) and a highly parametrized empirical exchange-correlation functional (M05-2X). The results were compared to X-ray structures and interaction energies reported in previous experimental and theoretical studies. It was found that B3LYP and CAM-B3LYP functionals fail to reproduce the X-ray structures and binding energies of the TPP···C60 system. DFT-D functionals overestimated the π···π energy interactions for both systems, however, the optimized structures agree well with those observed experimentally. The LC-BLYP functional predicts geometries similar to X-ray structures; nevertheless, due to the lack of correction in the dispersion energy, the predicted energies for both model systems are low. On the other hand, the M05-2X functional exhibited the best performance. Both the structures and binding energies calculated with M05-2X are consistent with experimental and theoretical evidence reported by other authors, as well as with our experimental results obtained by means of atomic force microscopy on H2TPP thin films grown on the HOPG/C60 substrate by physical vapor deposition.