Garrettmunn7084

A sensitivity analysis is proposed to identify the microstates of an MSM that contribute most to the error in conjunction with the transition-based reweighting analysis method for a more efficient and accurate MSM construction.Hybrid osmotic Monte Carlo simulations were performed to anticipate the tunability of the separation performance of the flexible Zeolitic Imidazole Framework-8 (ZIF-8) via the application of an external mechanical pressure. This synergistic combination of mechanical control of the pore aperture/cage dimension and guest adsorption was applied to the challenging hexane isomers separation processes of vital importance in the field of petrochemical industry. The application of a mechanical pressure above 1 GPa was predicted to boost the linear hexane/2-methylpentane and 2-methylpentane/2,3-dimethylbutane selectivity by 40% and 17%, respectively, as compared to the pristine ZIF-8. We further unraveled the microscopic origin of this optimized performance with an in-depth analysis of the critical interplay between the structural changes of the ZIF-8 framework and the conformational rearrangements of C6 isomers under mechanical pressure.Two-dimensional electron-electron double resonance (2D-ELDOR) provides extensive insight into molecular motions. Recent developments permitting experiments at higher frequencies (95 GHz) provide molecular orientational resolution, enabling a clearer description of the nature of the motions. In previous work, we provided simulations for the case of domain motions within proteins that are themselves slowly tumbling in a solution. In order to perform these simulations, it was found that the standard approach of solving the relevant stochastic Liouville equation using the efficient Lanczos algorithm for this case breaks down, so algorithms were employed that rely on the Arnoldi iteration. While they lead to accurate simulations, they are very time-consuming. In this work, we focus on a variant known as the rational Arnoldi algorithm. We show that this can achieve a significant reduction in computation time. The stochastic Liouville matrix, which is of very large dimension, N, is first reduced to a much smaller dimension, m, e.g., from N ∼ O(104) to m ∼ 60, that spans the relevant Krylov subspace from which the spectrum is predicted. This requires the selection of the m frequency shifts to be utilized. A method of adaptive shift choice is introduced to optimize this selection. We also find that these procedures help in optimizing the pruning procedure that greatly reduces the dimension of the initial N dimensional stochastic Liouville matrix in such subsequent computations.Potential energy surfaces for high-energy collisions between an oxygen molecule and a nitrogen atom are useful for modeling chemical dynamics in shock waves. In the present work, we present doublet, quartet, and sextet potential energy surfaces that are suitable for studying collisions of O2(3Σg-) with N(4S) in the electronically adiabatic approximation. Two sets of surfaces are developed, one using neural networks (NNs) with permutationally invariant polynomials (PIPs) and one with the least-squares many-body (MB) method, where a two-body part is an accurate diatomic potential and the three-body part is expressed with connected PIPs in mixed-exponential-Gaussian bond order variables (MEGs). We find, using the same dataset for both fits, that the fitting performance of the PIP-NN method is significantly better than that of the MB-PIP-MEG method, even though the MB-PIP-MEG fit uses a higher-order PIP than those used in previous MB-PIP-MEG fits of related systems (such as N4 and N2O2). However, the evaluation of the PIP-NN fit in trajectory calculations requires about 5 times more computer time than is required for the MB-PIP-MEG fit.Infrared spectroscopy is a widely used technique to characterize protein structures and protein mediated processes. While the amide I band provides information on proteins' secondary structure, amino acid side chains are used as infrared probes for the investigation of protein reactions and local properties. In this paper, we use a hybrid quantum mechanical/classical molecular dynamical approach based on the perturbed matrix method to compute the infrared band due to the C=O stretching mode of amide-containing side chains. We calculate, at first, the infrared band of zwitterionic glutamine in water and obtain results in very good agreement with the experimental data. Then, we compute the signal arising from glutamine side chains in a microcrystal of the yeast prion Sup35-derived peptide, GNNQQNY, with a fibrillar structure. The infrared bands obtained by selective isotopic labeling of the two glutamine residues, Q4 and Q5, of each peptide were experimentally used to investigate the local hydration in the fibrillar microcrystal. The experimental spectra of the two glutamine residues, which experience different hydration environments, feature different spectral signals that are well reproduced by the corresponding calculated spectra. In addition, the analysis of the simulated spectra clarifies the molecular origin of the experimentally observed spectroscopic differences that arise from the different local electric field experienced by the two glutamine residues, which is, in turn, determined by a different hydrogen bonding pattern.Hydrated molecular anions are present in the atmosphere. https://www.selleckchem.com/products/BIBF1120.html Revealing the structure of the microsolvation is key to understanding their chemical properties. The infrared spectra of CO3•-(H2O)1,2 and CO4•-(H2O)1,2 were measured via infrared multiple photon dissociation spectroscopy in both warm and cold environments. Redshifted from the free O-H stretch frequency, broad, structured spectra were observed in the O-H stretching region for all cluster ions, which provide information on the interaction of the hydrogen atoms with the central ion. In the C-O stretching region, the spectra exhibit clear maxima, but dissociation of CO3•-(H2O)1,2 was surprisingly inefficient. While CO3•-(H2O)1,2 and CO4•-(H2O) dissociate via loss of water, CO2 loss is the dominant dissociation channel for CO4•-(H2O)2. The experimental spectra are compared to calculated spectra within the harmonic approximation and from analysis of molecular dynamics simulations. The simulations support the hypothesis that many isomers contribute to the observed spectrum at finite temperatures. The highly fluxional nature of the clusters is the main reason for the spectral broadening, while water-water hydrogen bonding seems to play a minor role in the doubly hydrated species.Investigation of ion transport through nanopores with highly overlapping electric double layers is extremely challenging. This can be attributed to the non-linear Poisson-Boltzmann equation that governs the behavior of the electrical potential distribution as well as other characteristics of ion transport. In this work, we leverage the approach of Schnitzer and Yariv [Phys. Rev. E 87, 054301 (2013)] to reduce the complexity of the governing equation. An asymptotic solution is derived, which shows remarkable correspondence to simulations of the non-approximated equations. This new solution is leveraged to address a number of highly debated issues. We derive the equivalent of the Gouy-Chapman equation for systems with highly overlapping electric double layers. This new relationship between the surface charge density and the surface potential is then utilized to determine the power-law scaling of nanopore conductances as a function of the bulk concentrations. We derive the coefficients of transport for the case of overlapping electric double layers and compare it to the renowned uniform potential model. We show that the uniform potential model is only an approximation for the exact solution for small surface charges. The findings of this work can be leveraged to uncover additional hidden attributes of ion transport through nanopores.X-ray absorption creates electron vacancies in the core shell. These highly excited states often relax by Auger decay-an autoionization process in which one valence electron fills the core hole and another valence electron is ejected into the ionization continuum. Despite the important role of Auger processes in many experimental settings, their first-principles modeling is challenging, even for small systems. The difficulty stems from the need to describe many-electron continuum (unbound) states, which cannot be tackled with standard quantum-chemistry methods. We present a novel approach to calculate Auger decay rates by combining Feshbach-Fano resonance theory with the equation-of-motion coupled-cluster single double (EOM-CCSD) framework. We use the core-valence separation scheme to define projectors into the bound (square-integrable) and unbound (continuum) subspaces of the full function space. The continuum many-body decay states are represented by products of an appropriate EOM-CCSD state and a free-electron state, described by a continuum orbital. The Auger rates are expressed in terms of reduced quantities, two-body Dyson amplitudes (objects analogous to the two-particle transition density matrix), contracted with two-electron bound-continuum integrals. Here, we consider two approximate treatments of the free electron a plane wave and a Coulomb wave with an effective charge, which allow us to evaluate all requisite integrals analytically; however, the theory can be extended to incorporate a more sophisticated description of the continuum orbital.An alternative combinatorial expression is presented for the Wigner numbers Wm,nJ that leads to a generating function and to several new identities. An extended class of Wigner numbers, Wigner numbers of the ℓth order, Wm,nJ,ℓ, is also introduced.We introduce a simple and effective method to decompose the energy dissipation in the dynamics of open quantum systems into contributions due to individual bath components. The method is based on a vibronic extension of the Förster resonance energy transfer theory that enables quantifying the energy dissipated by specific bath degrees of freedom. Its accuracy is determined by benchmarking against mixed quantum-classical simulations that reveal that the method provides a semi-quantitative frequency-dependent decomposition of the overall dissipation. The utility of the method is illustrated by using a model donor-acceptor pair interacting to a thermal harmonic bath with different coupling strengths. The method can be used to identify the key features of a bath that leads to energy dissipation as required to develop a deep understanding of the dynamics of open quantum systems and to engineer environments with desired dissipative features.Transport of ions through liquid-liquid interfaces is of fundamental importance to a wide variety of applications. However, since it is quite challenging for experimentalists to directly and selectively observe molecules at the interfaces, microscopic mechanisms of ion transport have been largely presumed from kinetic information. This Perspective illustrates recent examples that molecular dynamics simulations with proper free energy surfaces clarified mechanistic pictures of ion transport. The key is a proper choice of coordinates and defining/calculating free energy surfaces in multidimensional space. Once the free energy surfaces for realistic systems are available, they naturally provide new insight into the ion transport in unprecedented details, including water finger, transient ion pairing, and electron transfer.