Systematic Bottom-Up Molecular Coarse-Graining via Force Matching using Anisotropic Particles

We derive a systematic and general method for parametrizing coarse-grained molecular models consisting of anisotropic particles from fine-grained (e.g. all-atom) models for condensed-phase molecular dynamics simulations. The method, which we call anisotropic force-matching coarse-graining (AFM-CG), is based on rigorous statistical mechanical principles, enforcing consistency between the coarse-grained and fine-grained phase-space distributions to derive equations for the coarse-grained forces, masses, and moments of inertia in terms of properties of a condensed-phase fine-grained system. We verify the accuracy and efficiency of the method by coarse-graining liquid-state systems of two different anisotropic organic molecules, benzene and perylene, and show that the parametrized coarse-grained models more accurately describe properties of these systems than previous anisotropic coarse-grained models parametrized using other methods that do not account for finite-temperature and many-body effects on the condensed-phase coarse-grained interactions. The AFM-CG method will be useful for developing accurate and efficient dynamical simulation models of condensed-phase systems of molecules consisting of large, rigid, anisotropic fragments, such as nucleic acids, liquid crystals, and organic semiconductors.

Environmentally persistent free radicals in indoor particulate matter, dust, and on surfaces

Environmentally persistent free radicals (EPFR) are an emerging class of constituents in particulate matter (PM). They are relatively stable with lifetimes of days to years in the condensed phase, influence...

Inhomogeneous pion condensed phase hosting topologically stable baryons

We discuss the inhomogeneous pion condensed phase within the framework of chiral perturbation theory. We show how the general expression of the condensate can be obtained solving three coupled differential equations, expressing how the pion fields are modulated in space. Upon using some simplifying assumptions, we determine an analytic solution in (3+1)-dimensions. The obtained inhomogeneous condensate is characterized by a non-vanishing topological charge, which can be identified with the baryonic number. In this way, we obtain an inhomogeneous system of pions hosting an arbitrary number of baryons at fixed position in space.

Understanding the solid state luminescence and piezochromic properties in polymorphs of an anthracene derivative.

Luminescent molecular crystals have gained significant research interest for optoelectronic applications. However, fully understanding their structural and electronic relationships in the condensed phase and under external stimuli remains a significant...

ON ESTIMATION OF THE AREA PER A SURFACTANT MOLECULE IN A 2D MONOLAYER DURING THE LIQUID-EXPANDED-LIQUID-CONDENSED PHASE TRANSITION AT THE AIR/WATER INTERFACE

Предложен метод оценки площади A, приходящейся на молекулу монослоя ПАВ, вначале перехода от жидко-растянутой к жидко-конденсированной фазе на основе двух теоретических моделей. Термодинамическая модель поведения дифильных монослоев с учетом неидеальности энтропии смешения позволяет оценить величину энергий Гиббса кластеризации ПАВ на основе П-А-изотерм, полученных при различных температурах. С другой стороны квантово-химический подход также дает возможность рассчитать данный термодинамический параметр и оценить структурные особенности получаемых монослоев. Величины энергий Гиббса кластеризации малых ассоциатов ПАВ и геометрических параметров элементарных ячеек монослоев были рассчитаны ранее с помощью квантово-химического полуэмпирического метода РМ3 для восьми классов дифильных соединений: насыщенные и этоксилированные спирты, насыщенные и цис-моноеновые карбоновые кислоты, α -гидрокси- и α -аминокислоты, N -ацилпроизводные аланина и диалкилзамещенные меламина. Эти параметры были использованы в термодинамической модели с учетом неидеальности энтропии смешения для расчета величин A. Оцененные значения A адекватно отражают экспериментальную температурную зависимость для рассматриваемого фазового перехода: с ростом температуры площадь, приходящаяся на молекулу ПАВ фиксированной длины цепи, уменьшается, и, наоборот, с ростом длины цепи ПАВ при фиксированной температуре величина A увеличивается. Это позволяет использовать предложенный подход в прогностических целях. A method is proposed to estimate the area per molecule of a surfactant monolayer A at the transition onset of the liquid-expanded to a liquid-condensed phase based on two theoretical models. A thermodynamic model with account for nonideality of the mixing entropy makes it possible to estimate the Gibbs energy of surfactant clusterization using the П-A isotherms obtained at different temperatures. On the other hand, the quantum-chemical approach also makes it possible to calculate this thermodynamic parameter and assess the structural features of the obtained monolayers. The values of the Gibbs clusterization energies of small surfactant associates and the geometric parameters of the monolayer unit cells were previously calculated using the quantum-chemical semiempirical method PM3 for eight classes of amphiphilic compounds: saturated and ethoxylated alcohols, saturated and cis-monoenic carboxylic acids, α-hydroxylic and α-amino acids, N -acyl-substituted alanines and dialkyl-substituted melamine. These parameters are used in the thermodynamic model with account for nonideality of the mixing entropy to calculate A. The estimated values Aadequately reflect the experimental temperature dependence for the considered phase transition: with an increase in temperature the area per surfactant molecule of a fixed chain length decreases, and vice versa, with an increase in the surfactant chain length at a fixed temperature, the value A increases. This makes it possible to use the proposed approach for prognostic purposes.

Soot Formation Numerical Simulation in Reducing Gas Generators of Oxygen-Methane Liquid Rocket Engines

A method for numerical simulation of operating processes in reducing gas generators with calculation of the condensed phase (soot) formation process detailed structure has been developed. It is assumed that soot is formed from gas-phase fuel in two stages. At the first stage, active radical nuclei are formed, and at the second stage, carbon black particles are formed from these nuclei. Numerical modeling of processes, fuel mixing and combustion, as well as soot formation in model reducing oxygen-methane gas generators with gas-liquid coaxial mixing elements of jet-jet type has been performed. Gas generators of this type can be used in promising oxygen-methane liquid rocket engines operating on open and closed circuits with reducing gas generators, as well as on the gas-gas circuit having reducing and oxidizing gas generators. A comparative analysis of soot formation features in gas generators with single- and multi-nozzle mixing heads has been performed. It is shown that a decrease in the pitch between the mixing elements leads to a significant change in the mixture formation processes, fuel combustion and the flow of combustion products (all other conditions being equal), which significantly reduces the intensity of condensed phase formation in reducing gas generators. The numerical simulation method will be used for studies of fuel combustion and condensed phase formation in regenerative gas generators of modern and advanced liquid rocket engines at the stages of development, design and improvement