Comparison of Model Chemistry and Density Functional Theory Thermochemical Predictions with Experiment for Formation of Ionic Clusters of the Ammonium Cation Complexed with Water and Ammonia; Atmospheric Implications

The G2, G3, CBS-QB3, and CBS-APNO model chemistry methods and the B3LYP, B3P86, mPW1PW, and PBE1PBE density functional theory (DFT) methods have been used to calculate ΔH° and ΔG° values for ionic clusters of the ammonium ion complexed with water and ammonia. Results for the clusters NH4+(NH3)n and NH4+(H2O)n, where n = 1−4, are reported in this paper and compared against experimental values. Agreement with the experimental values for ΔH° and ΔG° for formation of NH4+(NH3)n clusters is excellent. Comparison between experiment and theory for formation of the NH4+(H2O)n clusters is quite good considering the uncertainty in the experimental values. The four DFT methods yield excellent agreement with experiment and the model chemistry methods when the aug-cc-pVTZ basis set is used for energetic calculations and the 6-31G* basis set is used for geometries and frequencies. On the basis of these results, we predict that all ions in the lower troposphere will be saturated with at least one complete first hydration shell of water molecules.

Modern charge density studies: the entanglement of experiment and theory

This tutorial review article is intended to provide a general guidance to a reader interested to learn about the methodologies to obtain accurate electron density mapping in molecules and crystalline solids, from theory or from experiment, and to carry out a sensible interpretation of the results, for chemical, biochemical or materials science applications. The review mainly focuses on X-ray diffraction techniques and refinement of experimental models, in particular multipolar models. Neutron diffraction, which was widely used in the past to fix accurate positions of atoms, is now used for more specific purposes. The review illustrates three principal analyses of the experimental or theoretical electron density, based on quantum chemical, semi-empirical or empirical interpretation schemes, such as the quantum theory of atoms in molecules, the semi-classical evaluation of interaction energies and the Hirshfeld analysis. In particular, it is shown that a simple topological analysis based on a partition of the electron density cannot alone reveal the whole nature of chemical bonding. More information based on the pair density is necessary. A connection between quantum mechanics and observable quantities is given in order to provide the physical grounds to explain the observations and to justify the interpretations.

Revival of oscillation from mean-field-induced death : Theory and experiment

Submitted ACKNOWLEDGMENTS T. B. acknowledges the financial support from SERB, Department of Science and Technology (DST), India [Project Grant No.: SB/FTP/PS-005/2013]. D. G. acknowledges DST, India, for providing support through the INSPIRE fellowship. J. K. acknowledges Government of the Russian Federation (Agreement No. 14.Z50.31.0033 with Institute of Applied Physics RAS).

The elasticity and failure of fluid-filled cellular solids: Theory and experiment

We extend and apply theories of filled foam elasticity and failure to recently available data on foods. The predictions of elastic modulus and failure mode dependence on internal pressure and on wall integrity are borne out by photographic evidence of distortion and failure under compressive loading and under the localized stress applied by a knife blade, and by mechanical data on vegetables differing only in their turgor pressure. We calculate the dry modulus of plate-like cellular solids and the cross over between dry-like and fully fluid-filled elastic response. The bulk elastic properties of limp and aging cellular solids are calculated for model systems and compared with our mechanical data, which also show two regimes of response. The mechanics of an aged, limp beam is calculated, thus offering a practical procedure for comparing experiment and theory. This investigation also thereby offers explanations of the connection between turgor pressure and crispness and limpness of cellular materials.

The vibrational energy flow transition in organic molecules: Theory meets experiment

Most large dynamical systems are thought to have ergodic dynamics, whereas small systems may not have free interchange of energy between degrees of freedom. This assumption is made in many areas of chemistry and physics, ranging from nuclei to reacting molecules and on to quantum dots. We examine the transition to facile vibrational energy flow in a large set of organic molecules as molecular size is increased. Both analytical and computational results based on local random matrix models describe the transition to unrestricted vibrational energy flow in these molecules. In particular, the models connect the number of states participating in intramolecular energy flow to simple molecular properties such as the molecular size and the distribution of vibrational frequencies. The transition itself is governed by a local anharmonic coupling strength and a local state density. The theoretical results for the transition characteristics compare well with those implied by experimental measurements using IR fluorescence spectroscopy of dilution factors reported by Stewart and McDonald [Stewart, G. M. & McDonald, J. D. (1983) J. Chem. Phys. 78, 3907–3915].

Stabilizing and Modulating Color by Copigmentation: Insights from Theory and Experiment

Natural anthocyanin pigments/dyes and phenolic copigments/co-dyes form noncovalent complexes, which stabilize and modulate (in particular blue, violet, and red) colors in flowers, berries, and food products derived from them (including wines, jams, purees, and syrups). This noncovalent association and their electronic and optical implications constitute the copigmentation phenomenon. Over the past decade, experimental and theoretical studies have enabled a molecular understanding of copigmentation. This review revisits this phenomenon to provide a comprehensive description of the nature of binding (the dispersion and electrostatic components of π–π stacking, the hydrophobic effect, and possible hydrogen-bonding between pigment and copigment) and of spectral modifications occurring in copigmentation complexes, in which charge transfer plays an important role. Particular attention is paid to applications of copigmentation in food chemistry.

Critical Temperature of a Trapped Bose Gas: Comparison of Theory and Experiment

We apply the projected Gross-Pitaevskii equation (PGPE) formalism to the experimental problem of the shift in critical temperature T-c of a harmonically confined Bose gas as reported in Gerbier , Phys. Rev. Lett. 92, 030405 (2004). The PGPE method includes critical fluctuations and we find the results differ from various mean-field theories, and are in best agreement with experimental data. To unequivocally observe beyond mean-field effects, however, the experimental precision must either improve by an order of magnitude, or consider more strongly interacting systems. This is the first application of a classical field method to make quantitative comparison with experiment.

Longitudinal parametric oscillation in photorefractive sillenites: comparison between theory and experiment

By using an alternative setup for photorefractive parametric oscillation in which wave mixing between the recording beams is avoided it has become possible to make more detailed comparisons with the space-charge wave theory. In the present paper we compare the experimental features of longitudinal parametric oscillation observed in a crystal of Bi12SiO20 with the theoretical predictions.

Longitudinal parametric oscillation in photorefractive sillenites: comparison between theory and experiment

By using an alternative setup for photorefractive parametric oscillation in which wave mixing between the recording beams is avoided it has become possible to make more detailed comparisons with the space-charge wave theory. In the present paper we compare the experimental features of longitudinal parametric oscillation observed in a crystal of Bi12SiO20 with the theoretical predictions.

One-dimensional optical wave turbulence:experiment and theory

We present a review of the latest developments in one-dimensional (1D) optical wave turbulence (OWT). Based on an original experimental setup that allows for the implementation of 1D OWT, we are able to show that an inverse cascade occurs through the spontaneous evolution of the nonlinear field up to the point when modulational instability leads to soliton formation. After solitons are formed, further interaction of the solitons among themselves and with incoherent waves leads to a final condensate state dominated by a single strong soliton. Motivated by the observations, we develop a theoretical description, showing that the inverse cascade develops through six-wave interaction, and that this is the basic mechanism of nonlinear wave coupling for 1D OWT. We describe theory, numerics and experimental observations while trying to incorporate all the different aspects into a consistent context. The experimental system is described by two coupled nonlinear equations, which we explore within two wave limits allowing for the expression of the evolution of the complex amplitude in a single dynamical equation. The long-wave limit corresponds to waves with wave numbers smaller than the electrical coherence length of the liquid crystal, and the opposite limit, when wave numbers are larger. We show that both of these systems are of a dual cascade type, analogous to two-dimensional (2D) turbulence, which can be described by wave turbulence (WT) theory, and conclude that the cascades are induced by a six-wave resonant interaction process. WT theory predicts several stationary solutions (non-equilibrium and thermodynamic) to both the long- and short-wave systems, and we investigate the necessary conditions required for their realization. Interestingly, the long-wave system is close to the integrable 1D nonlinear Schrödinger equation (NLSE) (which contains exact nonlinear soliton solutions), and as a result during the inverse cascade, nonlinearity of the system at low wave numbers becomes strong. Subsequently, due to the focusing nature of the nonlinearity, this leads to modulational instability (MI) of the condensate and the formation of solitons. Finally, with the aid of the probability density function (PDF) description of WT theory, we explain the coexistence and mutual interactions between solitons and the weakly nonlinear random wave background in the form of a wave turbulence life cycle (WTLC).

Ionospheric Turbulence Near the Upper Hybrid Layer: Theory and Experiment

The thesis presents experimental results, simulations, and theory on turbulence excited in magnetized plasmas near the ionosphere’s upper hybrid layer. The results include: The first experimental observations of super small striations (SSS) excited by the High-Frequency Auroral Research Project (HAARP) The first detection of high-frequency (HF) waves from the HAARP transmitter over a distance of 16x10^3 km The first simulations indicating that upper hybrid (UH) turbulence excites electron Bernstein waves associated with all nearby gyroharmonics Simulation results that indicate that the resulting bulk electron heating near the upper hybrid (UH) resonance is caused primarily by electron Bernstein waves parametrically excited near the first gyroharmonic. On the experimental side we present two sets of experiments performed at the HAARP heating facility in Alaska. In the first set of experiments, we present the first detection of super-small (cm scale) striations (SSS) at the HAARP facility. We detected density structures smaller than 30 cm for the first time through a combination of satellite and ground based measurements. In the second set of experiments, we present the results of a novel diagnostic implemented by the Ukrainian Antarctic Station (UAS) in Verdansky. The technique allowed the detection of the HAARP signal at a distance of nearly 16 Mm, and established that the HAARP signal was injected into the ionospheric waveguide by direct scattering off of dekameter-scale density structures induced by the heater. On the theoretical side, we present results of Vlasov simulations near the upper hybrid layer. These results are consistent with the bulk heating required by previous work on the theory of the formation of descending artificial ionospheric layers (DIALs), and with the new observations of DIALs at HAARP’s upgraded effective radiated power (ERP). The simulations that frequency sweeps, and demonstrate that the heating changes from a bulk heating between gyroharmonics, to a tail acceleration as the pump frequency is swept through the fourth gyroharmonic. These simulations are in good agreement with experiments. We also incorporate test particle simulations that isolate the effects of specific wave modes on heating, and we find important contributions from both electron Bernstein waves and upper hybrid waves, the former of which have not yet been detected by experiments, and have not been previously explored as a driver of heating. In presenting these results, we analyzed data from HAARP diagnostics and assisted in planning the second round of experiments. We integrated the data into a picture of experiments that demonstrated the detection of SSS, hysteresis effects in simulated electromagnetic emission (SEE) features, and the direct scattering of the HF pump into the ionospheric waveguide. We performed simulations and analyzed simulation data to build the understanding of collisionless heating near the upper hybrid layer, and we used these simulations to show that bulk electron heating at the upper hybrid layer is possible, which is required by current theories of DAIL formation. We wrote a test particle simulation to isolate the effects of electron Bernstein waves and upper hybrid layers on collisionless heating, and integrated this code to work with both the output of Vlasov simulations and the input for simulations of DAIL formation.