Klavsenmiranda0868

We study the sensitivity and practicality of Henderson's theorem in classical statistical mechanics, which states that the pair potential v(r) that gives rise to a given pair correlation function g2(r) [or equivalently, the structure factor S(k)] in a classical many-body system at number density ρ and temperature T is unique up to an additive constant. While widely invoked in inverse-problem studies, the utility of the theorem has not been quantitatively scrutinized to any large degree. We show that Henderson's theorem has practical shortcomings for disordered and ordered phases for certain densities and temperatures. Using proposed sensitivity metrics, we identify illustrative cases in which distinctly different potential functions give very similar pair correlation functions and/or structure factors up to their corresponding correlation lengths. Our results reveal that due to a limited range and precision of pair information in either direct or reciprocal space, there is effective ambiguity of solutions to inverse problems that utilize pair information only, and more caution must be exercised when one claims the uniqueness of any resulting effective pair potential found in practice. We have also identified systems that possess virtually identical pair statistics but have distinctly different higher-order correlations. Such differences should be reflected in their individually distinct dynamics (e.g., glassy behaviors). Finally, we prove a more general version of Henderson's theorem that extends the uniqueness statement to include potentials that involve two- and higher-body interactions.Permeation of many small molecules through lipid bilayers can be directly observed in molecular dynamics simulations on the nano- and microsecond timescale. While unbiased simulations provide an unobstructed view of the permeation process, their feasibility for computing permeability coefficients depends on various factors that differ for each permeant. The present work studies three small molecules for which unbiased simulations of permeation are feasible within less than a microsecond, one hydrophobic (oxygen), one hydrophilic (water), and one amphiphilic (ethanol). Permeabilities are computed using two approaches counting methods and a maximum-likelihood estimation for the inhomogeneous solubility diffusion (ISD) model. Counting methods yield nearly model-free estimates of the permeability for all three permeants. While the ISD-based approach is reasonable for oxygen, it lacks precision for water due to insufficient sampling and results in misleading estimates for ethanol due to invalid model assumptions. It is also demonstrated that simulations using a Langevin thermostat with collision frequencies of 1/ps and 5/ps yield oxygen permeabilities and diffusion constants that are lower than those using Nosé-Hoover by statistically significant margins. In contrast, permeabilities from trajectories generated with Nosé-Hoover and the microcanonical ensemble do not show statistically significant differences. As molecular simulations become more affordable and accurate, calculation of permeability for an expanding range of molecules will be feasible using unbiased simulations. The present work summarizes theoretical underpinnings, identifies pitfalls, and develops best practices for such simulations.We introduce a new theoretical and computational framework for treating molecular quantum mechanics without the Born-Oppenheimer approximation. The molecular wavefunction is represented in a tensor-product space of electronic and vibrational basis functions, with electronic basis chosen to reproduce the mean-field electronic structure at all geometries. We show how to transform the Hamiltonian to a fully second-quantized form with creation/annihilation operators for electronic and vibrational quantum particles, paving the way for polynomial-scaling approximations to the tensor-product space formalism. In addition, we make a proof-of-principle application of the new Ansatz to the vibronic spectrum of C2.The quantum many-body problem in condensed phases is often simplified using a quasiparticle description, such as effective mass theory for electron motion in a periodic solid. These approaches are often the basis for understanding many fundamental condensed phase processes, including the molecular mechanisms underlying solar energy harvesting and photocatalysis. Despite the importance of these effective particles, there is still a need for computational methods that can explore their behavior on chemically relevant length and time scales. This is especially true when the interactions between the particles and their environment are important. We introduce an approach for studying quasiparticles in condensed phases by combining effective mass theory with the path integral treatment of quantum particles. This framework incorporates the generally anisotropic electronic band structure of materials into path integral simulation schemes to enable modeling of quasiparticles in quantum confinement, for example. We demonstrate the utility of effective mass path integral simulations by modeling an exciton in solid potassium chloride and electron trapping by a sulfur vacancy in monolayer molybdenum disulfide.The near-field properties and dynamics of plasmonic nanostructures play a crucial role in several fundamental concepts in physics and chemistry, and they are widely relevant in plasmonic applications. Ultrafast photoemission electron microscopy (PEEM) is a novel approach that has been widely applied to probe plasmonic nanostructures from multiple domains. Furthermore, PEEM is the only technique that provides nanometer spatial resolution, sub-femtosecond temporal resolution, and tens to hundreds of millielectron volt energy resolution. This allows for extremely sensitive observations of plasmonic field oscillations, field dephasing, and hot electrons. This Perspective provides a brief overview of the basic principles and main applications of ultrafast PEEM. Linrodostat The research progress of ultrafast PEEM in plasmonics is highlighted from three points of view near-field imaging, near-field spectroscopy, and ultrafast dynamics. Future applications of PEEM in plasmonics for the probing of plasmonic hot electron dynamics in the energy and time domains are proposed and discussed.