Molecular Dynamics Simulations of Solutions at Constant Chemical Potential

Molecular Dynamics studies of chemical processes in solution are of great value in a wide spectrum of applications, which range from nano-technology to pharmaceutical chemistry. However, these calculations are affected by severe finite-size effects, such as the solution being depleted as the chemical process proceeds, which influence the outcome of the simulations. To overcome these limitations, one must allow the system to exchange molecules with a macroscopic reservoir, thus sampling a Grand-Canonical ensemble. Despite the fact that different remedies have been proposed, this still represents a key challenge in molecular simulations. In the present work we propose the Constant Chemical Potential Molecular Dynamics (C$\mu$MD) method, which introduces an external force that controls the environment of the chemical process of interest. This external force, drawing molecules from a finite reservoir, maintains the chemical potential constant in the region where the process takes place. We have applied the C$\mu$MD method to the paradigmatic case of urea crystallization in aqueous solution. As a result, we have been able to study crystal growth dynamics under constant supersaturation conditions, and to extract growth rates and free-energy barriers.Comment: 8 pages, 8 figures (Supplementary Information: 6 pages, 7 figures). Typos and labelling corrected Ver. 3: Minor comments added in Sec. 3. References 13,36,38 added. Minor text changes and typos correcte

Chemical Potential Calculations In Dense Liquids Using Metadynamics

The calculation of chemical potential has traditionally been a challenge in atomistic simulations. One of the most used approaches is Widom's insertion method in which the chemical potential is calculated by periodically attempting to insert an extra particle in the system. In dense systems this method fails since the insertion probability is very low. In this paper we show that in a homogeneous fluid the insertion probability can be increased using metadynamics. We test our method on a supercooled high density binary Lennard-Jones fluid. We find that we can obtain efficiently converged results even when Widom's method fails.Comment: 5 pages, 2 figures, Ver 2: typos corrected, Ref. 10 year correcte

Chemical Potential Calculations in Non-Homogeneous Liquids

The numerical computation of chemical potential in dense, non-homogeneous fluids is a key problem in the study of confined fluids thermodynamics. To this day several methods have been proposed, however there is still need for a robust technique, capable of obtaining accurate estimates at large average densities. A widely established technique is the Widom insertion method, that computes the chemical potential by sampling the energy of insertion of a test particle. Non-homogeneity is accounted for by assigning a density dependent weight to the insertion points. However, in dense systems, the poor sampling of the insertion energy is a source of inefficiency, hampering a reliable convergence. We have recently presented a new technique for the chemical potential calculation in homogeneous fluids. This novel method enhances the sampling of the insertion energy via Well-Tempered Metadynamics, reaching accurate estimates at very large densities. In this paper we extend the technique to the case of non-homogeneous fluids. The method is successfully tested on a confined Lennard-Jones fluid. In particular we show that, thanks to the improved sampling, our technique does not suffer from a systematic error that affects the classic Widom method for non-homogeneous fluids, providing a precise and accurate result.Comment: 16 pages, 4 figures Contains a Supplementary Information fil

Experimental Demonstration of Dual Polarization Nonlinear Frequency Division Multiplexed Optical Transmission System

Multi-eigenvalues transmission with information encoded simultaneously in both orthogonal polarizations is experimentally demonstrated. Performance below the HD-FEC limit is demonstrated for 8-bits/symbol 1-GBd signals after transmission up to 207 km of SSMF

Dual polarization nonlinear Fourier transform-based optical communication system

New services and applications are causing an exponential increase in internet traffic. In a few years, current fiber optic communication system infrastructure will not be able to meet this demand because fiber nonlinearity dramatically limits the information transmission rate. Eigenvalue communication could potentially overcome these limitations. It relies on a mathematical technique called "nonlinear Fourier transform (NFT)" to exploit the "hidden" linearity of the nonlinear Schr\"odinger equation as the master model for signal propagation in an optical fiber. We present here the theoretical tools describing the NFT for the Manakov system and report on experimental transmission results for dual polarization in fiber optic eigenvalue communications. A transmission of up to 373.5 km with bit error rate less than the hard-decision forward error correction threshold has been achieved. Our results demonstrate that dual-polarization NFT can work in practice and enable an increased spectral efficiency in NFT-based communication systems, which are currently based on single polarization channels

The role of oxygen vacancies on the structure and the density of states of iron doped zirconia

In this paper we study, both with theoretical and experimental approach, the effect of iron doping in zirconia. Combining density functional theory (DFT) simulations with the experimental characterization of thin films, we show that iron is in the Fe3+ oxidation state and accordingly that the films are rich in oxygen vacancies (VO). VO favor the formation of the tetragonal phase in doped zirconia (ZrO2:Fe) and affect the density of state at the Fermi level as well as the local magnetization of Fe atoms. We also show that the Fe(2p) and Fe(3p) energy levels can be used as a marker for the presence of vacancies in the doped system. In particular the computed position of the Fe(3p) peak is strongly sensitive to the VO to Fe atoms ratio. A comparison of the theoretical and experimental Fe(3p) peak position suggests that in our films this ratio is close to 0.5. Besides the interest in the material by itself, ZrO2:Fe constitutes a test case for the application of DFT on transition metals embedded in oxides. In ZrO2:Fe the inclusion of the Hubbard U correction significantly changes the electronic properties of the system. However the inclusion of this correction, at least for the value U = 3.3 eV chosen in the present work, worsen the agreement with the measured photo-emission valence band spectra.Comment: 24 pages, 8 figure

Late Holocene onset of intensive cultivation and introduction of the falaj irrigation system in the Salut oasis (Sultanate of Oman)

This paper discusses the time and steps of the introduction of intensive agriculture and evolution of irrigation systems to sustain crops in the palaeo-oasis of Salut in the northern Sultanate of Oman. Various geoarchaeological methods allow reconstructing the exploitation of the natural resources of the region and technological development of irrigation methods since the Mid-Holocene. Intensive agriculture started during the Bronze Age and continued with some spatial and intensity fluctuations up to the Islamic period. Cultivations were initially sustained by surface irrigation systems and later replaced by a dense net of aflaj, the typical surface/underground system adopted in the Levant, Arabian Peninsula and western Asia to collect water from deep piedmont aquifers and redistribute it to the fields located in the lowlands. Our results indicate that the aflaj were in use for a long period in the palaeo-oasis formed along Wadi Sayfam and surrounding the citadel of Salut. Uranium-Thorium dating of calcareous tufa formed in the underground tunnels of the aflaj suggests that they were used between ∼540 BCE and ∼1150 CE. After ∼1150 CE Wadi Sayfam were abandoned and the size of the oasis shrank substantially. During the late Islamic period, a surface aqueduct descending from the piedmont of Jabal Shams secured water supply. Our work confirms that in arid lands archaeological and historical communities were able to actively modulate their response to climate changes by using a variety of technological strategies

Ultrathin random copolymer-grafted layers for block copolymer self-assembly

Hydroxyl-terminated P(S-r-MMA) random copolymers (RCPs) with molecular weights (Mn) from 1700 to 69000 and a styrene unit fraction of approximately 61% were grafted onto a silicon oxide surface and subsequently used to study the orientation of nanodomains with respect to the substrate, in cylinder-forming PS-b-PMMA block copolymer (BCP) thin films. When the thickness (H) of the grafted layer is greater than 5-6 nm, a perpendicular orientation is always observed because of the efficient decoupling of the BCP film from the polar SiO2 surface. Conversely, if H is less than 5 nm, the critical thickness of the grafted layer, which allows the neutralization of the substrate and promotion of the perpendicular orientation of the nanodomains in the BCP film, is found to depend on the Mn of the RCP. In particular, when Mn = 1700, a 2.0 nm thick grafted layer is sufficient to promote the perpendicular orientation of the PMMA cylinders in the PS-b-PMMA BCP film. A proximity shielding mechanism of the BCP molecules from the polar substrate surface, driven by chain stretching of the grafted RCP molecules, is proposed