Vogelvaughan7876

Our calculated thermodynamics of reaction pathways lead to the conclusion that the Cu(111) substrate promotes both methanol and ethanol as the products, while kinetic Monte Carlo simulations suggest a high selectivity toward the formation of ethanol.Fourier transform infrared (FTIR) and two-dimensional IR (2D-IR) spectroscopies were applied to polydimethylsiloxane (PDMS) cross-linked elastomer films. The vibrational probe for the systems studied was a silicon hydride mode that was covalently bound to the polymer chains. The structure and dynamics reported by this mode were measured in response to a wide range of chemical and physical perturbations, including elevated curing temperature, increased curing agent concentration, mechanical compression, and cooling to near the glass transition temperature. The FTIR spectra were found to be relatively insensitive to all of these perturbations, and 2D-IR spectroscopy revealed that this was due to the overwhelming influence of heterogeneity on the spectral line shape. Surprisingly, the deconvoluted spectral line shapes showed that there were only slight differences in the heterogeneous and homogeneous dynamics even with the drastic macroscopic changes occurring in different systems. In the context of modeling polymer behavior, the results confirm that dynamics on the ultrafast time scale need not be included to properly model PDMS elasticity.Molecular modeling plays an important role in the discovery of organic structure-directing agents (OSDAs) for zeolites. By quantifying the intensity of host-guest interactions, it is possible to select cost-effective molecules that maximize binding toward a given zeolite framework. Over the last few decades, a variety of methods and levels of theory have been used to calculate these binding energies. Nevertheless, there is no consensus on the best calculation strategy for high-throughput virtual screening undertakings. In this work, we compare binding affinities from density functional theory (DFT) and Dreiding force field calculations for 272 zeolite-OSDA pairs obtained from static and time-averaged simulations. Enabled by automation software, we show that Dreiding binding energies from the frozen pose method correlate best with DFT energies. They are also less sensitive to the choice of initial lattice parameters and optimization algorithms, as well as less computationally expensive than their time-averaged counterparts. Furthermore, we demonstrate that a broader exploration of the conformation space from molecular dynamics simulations does not provide significant improvements in binding energy trends over the frozen pose method despite being orders of magnitude more expensive. The code and benchmark data are open-sourced and provide robust and computationally efficient guidelines to calculating binding energies in zeolite-OSDA pairs.In condensed molecular matter, low-frequency modes (LFMs) associated with specific molecular motions are excited at room temperature and determine essential physical and chemical properties of materials. LFMs, with typical mode energies of up to ∼500 cm-1 (62 meV), contribute significantly to thermodynamic parameters and functions (e.g., heat capacity and entropy) and constitute the basis for room temperature molecular dynamics (e.g., conformational fluctuations and change). LFMs are often analyzed indirectly by the measurement of their effect on specific high-frequency modes (HFMs); the LFM-HFM coupling is reflected in the lineshape, as well as in the spectral and angular diffusion of the HFM. Two-dimensional terahertz-infrared-visible (2D TIRV) spectroscopy allows measuring the LFM-HFM coupling directly and can thereby provide new insights into the strength and nature of the coupling and the character of LFMs. However, the interference between the different signals generated by different excitation pathways can complicate 2D TIRV spectra, preventing a straightforward analysis. Proxalutamide Here, we develop an experimental method to distinguish different excitation pathways in 2D TIRV spectroscopy and plot them separately in different quadrants of a 2D spectrum. We validate this method by measuring the spectra of CaF2 and nitrogen gas. For CaF2, only sum-frequency mixing between infrared and terahertz fields generates the signal. In contrast, for N2, only difference-frequency mixing is observed. We then use this method to separate sum- and difference-frequency pathways in the 2D TIRV spectrum of liquid water, verifying the previous interpretation of the lineshape of the 2D TIRV spectrum of water.Photodissociation of [Ar-N2]+ induced by a near-IR (800 nm) femtosecond laser pulse is investigated using ion-trap time-of-flight mass spectrometry. The intra-complex charge transfer proceeding in the course of the decomposition of the electronically excited Ar+(2P3/2)⋯N2(X1Σg +), prepared by the photoexcitation of the electronic ground Ar(1S0)⋯N2 +(X2Σg +), is probed by the ion yields of Ar+ and N2 +. The yield ratio γ of N2 + with respect to the sum of the yields of Ar+ and N2 + is determined to be γ = 0.62, which is much larger than γ ∼ 0.2 determined before when the photodissociation is induced by a nano-second laser pulse in the shorter wavelength region between 270 and 650 nm. This enhancement of γ at 800 nm and the dependence of γ on the excitation wavelength are interpreted by numerical simulations, in which the adiabatic population transfer from Ar+(2P3/2)⋯N2(X1Σg +) to Ar(1S0)⋯N2 +(X2Σg +) at the avoided crossings is accompanied by the vibrational excitation in the N2 +(X2Σg +) moiety followed by the intra-complex vibrational energy transfer from the N2 +(X2Σg +) moiety to the intra-complex vibrational mode leading to the dissociation.We demonstrate the applicability of the Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) method to the problem of computing ground states of one-dimensional chains of linear rotors with dipolar interactions. Specifically, we successfully obtain energies, entanglement entropies, and orientational correlations that are in agreement with the Density Matrix Renormalization Group (DMRG), which has been previously used for this system. We find that the entropies calculated by ML-MCTDH for larger system sizes contain nonmonotonicity, as expected in the vicinity of a second-order quantum phase transition between ordered and disordered rotor states. We observe that this effect remains when all couplings besides nearest-neighbor are omitted from the Hamiltonian, which suggests that it is not sensitive to the rate of decay of the interactions. In contrast to DMRG, which is tailored to the one-dimensional case, ML-MCTDH (as implemented in the Heidelberg MCTDH package) requires more computational time and memory, although the requirements are still within reach of commodity hardware.