We perform dynamics simulations of donor-bridge-acceptor triads following photoexcitation and correlate nuclear motions with the charge-transfer event using the short-time Fourier transform technique. Broadly, the porphyrin bridges undergo higher energy vibrations, whereas the fullerene acceptors undergo low energy modes. Aryl side groups exhibit torsional motions relative to the porphyrin. Aryl linkers between the bridge and acceptor are restricted from such motions and therefore express ring distortion modes. Finally, we find an amide linker mode that is directionally sensitive to electron motion. This work supports the notion of vibrationally coupled ultrafast charge transfer found in both experimental and theoretical studies and lays a foundational method for identifying key vibrational modes for parametrizing future theoretical models.The anisotropic properties of organic glasses produced by physical vapor deposition (PVD) depend upon substrate temperature and deposition rate. In recent work, it was shown for a liquid crystalline system that the anisotropic structure of the glass was controlled by a single combined variable as indicated by the observation of deposition rate-substrate temperature superposition (RTS). Here we test the utility of RTS for posaconazole, a molecule that does not form liquid crystals. We prepare glasses of posaconazole utilizing a range of deposition rates covering 2 orders of magnitude and an 18 K range in substrate temperature. We characterize the glasses using ellipsometry and X-ray scattering. Consistent with RTS, we find that decreasing the deposition rate has the same effect upon molecular orientation as increasing the substrate temperature during deposition. Thus, RTS can be used to predict and control the structure of glasses prepared at a wide range of deposition conditions. We use RTS to infer a characteristic time for molecular reorientation at the surface of posaconazole.We develop here a mixed quantum mechanical/molecular dynamics model to investigate charge-transfer dynamics in a set of large organic donor-bridge-acceptor triad molecules. Specifically, we are interested in the differences in electron and nuclear behavior relating to small changes in the molecular makeup of carotenoid-porphyrin-fullerene triads. Our model approximates excitation energies on the order of 1.9 eV which agree with absorption spectra for these triads and isolated porphyrins. Using electron population analysis, we monitor charge migration to the acceptor in time. Approximations of the charge transfer rates reveal ultrafast (picosecond scale) electron dynamics consistent with experimental literature.The underlying interactions in physical and biological systems often lead to a variety of behaviors and emergent states or phases. Under certain conditions, these phases can be transformed from one to another. The phase transition behaviors can be described by the bifurcation or catastrophe where different stable/unstable states can branch out or meet together with the birth of the new and death of the old states. Despite significant efforts, how the bifurcation and catastrophe actually occur dynamically and the associated mechanisms for nonequilibrium systems is still not very clear. As an example, we study the underlying mechanism of cell differentiation through bifurcations. Cell differentiation is one of the key fate decision making processes that cell faces. It is crucial for the development of multi-cellular organism. Under induction, gene regulation changes, or stochastic fluctuations, the cell fate decision making processes can exhibit different types of bifurcations or phase transitions. In order to understand the underlying mechanism, it is crucial to find out where and how the bifurcation occurs. However, this is still largely unknown. In this study, we found that the average of the curl flux as a major component of the driving force for the dynamics in addition to the landscape gradient and the associated entropy production rate both reach maximum near the bifurcation.  https://www.selleckchem.com/products/ly2874455.html  This indicates that the curl flux and entropy production rate may provide the dynamical and thermodynamic origins of the bifurcation/catastrophe or phase transitions for cell differentiation and this possibly applies to many other nonequilibrium active systems.The phenyl + ethylene (C6H5 + C2H4) reaction network was explored experimentally and theoretically to understand the temperature dependence of the reaction kinetics and product distribution under various temperature and pressure conditions. The flash photolysis apparatus combining laser absorbance spectroscopy (LAS) and time-resolved molecular beam mass spectrometry (MBMS) was used to study reactions on the C8H9 potential energy surface (PES). In LAS experiments, 505.3 nm laser light selectively probed C6H5 decay, and we measured the total C6H5 consumption rate coefficients in the intermediate temperature region (400-800 K), which connects previous experiments performed in high-temperature (pyrolysis) and low-temperature (cavity-ring-down methods) regions. From the quantum chemistry calculations by Tokmakov and Lin using the G2M(RCC5)//B3LYP method, we constructed a kinetic model and estimated phenomenological pressure-dependent rate coefficients, k(T, P), with the Arkane package in the reaction mechanism gen verified by the increase in the yield of the stabilized adduct from radical addition from 80.2% (800 K, 10 Torr) to 88.9% (800 K, 50 Torr), at the expense of styrene + H. The pressure-dependent model developed in this work is well validated by the LAS and MBMS measurements and gives a complete picture of the C6H5 + C2H4 reaction.The high resolution far-infrared spectrum of trans-butadiene has been reinvestigated by Fourier-transform spectroscopy at two synchrotron radiation facilities, SOLEIL and the Canadian Light Source, at temperatures ranging from 50 to 340 K. Beyond the well-studied bands, two new fundamental bands lying below 1100 cm-1, ν10 and ν24, have been assigned using a combination of cross-correlation (ASAP software) and Loomis-Wood type (LWWa software) diagrams. While the ν24 analysis was rather straightforward, ν10 exhibits obvious signs of a strong perturbation, presumably owing to interaction with the dark ν9 + ν12 state. Effective rotational constants have been derived for both the v10 = 1 and v24 = 1 states. Since only one weak, infrared active fundamental band (ν23) of trans-butadiene remains to be observed at high resolution in the far-infrared, searches for the elusive gauche conformer can now be undertaken with considerably greater confidence in the dense ro-vibrational spectrum of the trans form.