The Rotational Oscillations of Tetrahydrofuran in Tetrahydrofuran Clathrate Hydrate

1973 ◽  
Vol 51 (24) ◽  
pp. 4062-4071 ◽  
Author(s):  
D. D. Klug ◽  
E. Whalley
Keyword(s):  
Gas Phase ◽  
Low Frequency ◽  
Clathrate Hydrate ◽  
Water Molecules ◽  
Dielectric Measurements ◽  
Effective Dipole Moment ◽  
Orientational Disorder ◽  
Guest Molecules ◽  
Rotational Oscillations ◽  
Good Agreement

The absorptivity of tetrahydrofuran clathrate hydrate in the range 70–7 cm−1 has been measured at several temperatures in the range 17–80 K. There are two broad bands with maxima at 25 and 38 cm−1 which are due to the rotational oscillations of tetrahydrofuran molecules in their cages. The integrated absorptivity yields an effective dipole moment for the oscillation of 1.63 D, which is close to the gas-phase value. The negative second moment of the absorptivity yields the contribution 0.105 ± ~0.007 to the low-frequency refractive index, in good agreement with a less accurate value from dielectric measurements. The orientational disorder of the water molecules causes a distribution of potentials hindering the rotational oscillations of the guest molecules, and a detailed analysis of the shapes of the bands yields directly the distribution of force constants for the oscillations.

A Clathrate Hydrate of Cyclobutanone: Dielectric Relaxation of the Host and Guest Molecules

1971 ◽  
Vol 49 (8) ◽  
pp. 1243-1251 ◽  
Author(s):  
B. Morris ◽  
D. W. Davidson
Keyword(s):  
Low Frequency ◽  
Clathrate Hydrate ◽  
Water Molecules ◽  
Dielectric Study ◽  
Static Permittivity ◽  
Tetrahedral Symmetry ◽  
Absorption Region ◽  
Guest Molecules ◽  
Arrhenius Energy ◽  
Rotational Oscillations

A low-frequency dielectric study of (CH2)3CO•17H2O shows a water absorption region characteristic of a structure II clathrate hydrate which melts congruently at 0.0 °C. The relatively low Arrhenius energy of 6.5 kcal mol–1 is similar to that of acetone hydrate, for which new results are given. At low temperatures reorientation of encaged cyclobutanone molecules gives a very broad absorption region and a contribution to the static permittivity which falls with decrease of temperature. These properties are attributed to the effects of the electrostatic fields of the orientationally-disordered water molecules, which form the cages. Such fields distort the tetrahedral symmetry of the cages to an extent which varies greatly from cage to cage. The high permittivity (~3.6) at 4.2 °K probably arises from rotational oscillations at frequencies near 20 cm−1 of the guest molecules in shallow potential minima. This enhancement of polarizability removes the difficulty previously noted in the applicability of the Onsager cavity model to structure II hydrates. The dipole moment of cyclobutanone in cyclohexane solution was found to be 2.78 ± 0.02 D.

Modeling Dissociation Pressure of Semi-Clathrate Hydrate Systems Containing CO2, CH4, N2, and H2S in the Presence of Tetra-n-butyl Ammonium Bromide

2019 ◽  
Vol 44 (1) ◽  
pp. 15-28 ◽  
Author(s):  
Mohammad Mesbah ◽  
Ebrahim Soroush ◽  
Mashallah Rezakazemi
Keyword(s):  
Gas Phase ◽  
Mass Fraction ◽  
Guest Molecule ◽  
Clathrate Hydrate ◽  
Clathrate Hydrates ◽  
Ammonium Bromide ◽  
Guest Molecules ◽  
Dissociation Pressure ◽  
Tuning Parameters ◽  
Langmuir Adsorption

Abstract In this study, the phase equilibria of semi-clathrate hydrates of methane (CH4), carbon dioxide (CO2), nitrogen (N2), and hydrogen sulfide (H2S) in an aqueous solution of tetra-n-butyl ammonium bromide (TBAB) were modeled using a correlation based on a two-stage formation mechanism: a quasi-chemical reaction that forms basic semi-clathrate hydrates and adsorption of guest molecules in the linked cavities of the basic semi-clathrate hydrate. The adsorption of guest molecules was described by the Langmuir adsorption theory and the fugacity of the gas phase was calculated by Peng–Robinson (PR) equation of state (EOS). The water activity in the presence of TBAB was calculated using a correlation, dependent on temperature, the TBAB mass fraction, and the nature of the guest molecule. These equations were coupled together and form a correlation which was linked to a genetic algorithm for optimization of tuning parameters. The results showed an excellent agreement between model results and experimental data. In addition, an outlier diagnostic was performed for finding any possible doubtful data and assessing the applicability of the model. The results showed that more than 97 % of the data were reliable and they were in the applicability domain of the model.

The anomalous halogen bonding interactions between chlorine and bromine with water in clathrate hydrates

2017 ◽  
Vol 203 ◽  
pp. 61-77 ◽  
Author(s):  
Hana Dureckova ◽  
Tom K. Woo ◽  
Konstantin A. Udachin ◽  
John A. Ripmeester ◽  
Saman Alavi
Keyword(s):  
Ab Initio ◽  
Halogen Bonding ◽  
Chem Phys ◽  
Clathrate Hydrate ◽  
Clathrate Hydrates ◽  
Water Molecules ◽  
Guest Molecules ◽  
X Ray ◽  
Covalent Interaction ◽  
Water Oxygen

Clathrate hydrate phases of Cl2 and Br2 guest molecules have been known for about 200 years. The crystal structure of these phases was recently re-determined with high accuracy by single crystal X-ray diffraction. In these structures, the water oxygen–halogen atom distances are determined to be shorter than the sum of the van der Waals radii, which indicates the action of some type of non-covalent interaction between the dihalogens and water molecules. Given that in the hydrate phases both lone pairs of each water oxygen atom are engaged in hydrogen bonding with other water molecules of the lattice, the nature of the oxygen–halogen interactions may not be the standard halogen bonds characterized recently in the solid state materials and enzyme–substrate compounds. The nature of the halogen–water interactions for the Cl2 and Br2 molecules in two isolated clathrate hydrate cages has recently been studied with ab initio calculations and Natural Bond Order analysis (Ochoa-Resendiz et al. J. Chem. Phys. 2016, 145, 161104). Here we present the results of ab initio calculations and natural localized molecular orbital analysis for Cl2 and Br2 guests in all cage types observed in the cubic structure I and tetragonal structure I clathrate hydrates to characterize the orbital interactions between the dihalogen guests and water. Calculations with isolated cages and cages with one shell of coordinating molecules are considered. The computational analysis is used to understand the nature of the halogen bonding in these materials and to interpret the guest positions in the hydrate cages obtained from the X-ray crystal structures.

Three new olanzapine structures: the acetic acid monosolvate, and the propan-2-ol and propan-2-one hemisolvate monohydrates

2013 ◽  
Vol 69 (7) ◽  
pp. 781-786 ◽  
Author(s):  
Joanna Bojarska ◽  
Waldemar Maniukiewicz ◽  
Lesław Sieroń
Keyword(s):  
Acetic Acid ◽  
Crystal Structures ◽  
Molecular Conformation ◽  
Crystal Packing ◽  
Water Molecules ◽  
Orientational Disorder ◽  
Aromatic Fragment ◽  
Guest Molecules ◽  
Positional Disorder ◽  
Twofold Axis

The crystal structures of three new solvates of olanzapine [systematic name: 2-methyl-4-(4-methylpiperazin-1-yl)-10H-thieno[2,3-b][1,5]benzodiazepine], namely olanzapine acetic acid monosolvate, C17H20N4S·C2H4O2, (I), olanzapine propan-2-ol hemisolvate monohydrate, C17H20N4S·0.5C3H8O·H2O, (II), and olanzapine propan-2-one hemisolvate monohydrate, C17H20N4S·0.5C3H6O·H2O, (III), are presented and compared with other known olanzapine forms. There is a fairly close resemblance of the molecular conformation for all studied analogues. The crystal structures are built up through olanzapine dimers, which are characterizedviaC—H...π interactions between the aliphatic fragment (1-methylpiperazin-4-yl) and the aromatic fragment (benzene system). All solvent (guest) molecules participate in hydrogen-bonding networks. The crystal packing is sustainedviaintermolecular Nhost—H...Oguest, Oguest—H...Nhost, Oguest—H...Oguestand Chost—H...Oguesthydrogen bonds. It should be noted that the solvent propan-2-ol in (II) and propan-2-one in (III) show orientational disorder. The propan-2-ol molecule lies close to a twofold axis, while the propan-2-one molecule resides strictly on a twofold axis through the carbonyl C atom. In both cases, the water molecules present positional disorder of the H atoms.

COMPUTER MODELING OF CHEMICAL EQUILIBRIUMS IN WO3–H2O SYSTEM

2017 ◽  
pp. 35-48 ◽  
Author(s):  
V.P. Bondarenko ◽  
O.O. Matviichuk
Keyword(s):  
Transition Temperature ◽  
Gas Phase ◽  
Single Phase ◽  
Reference Data ◽  
Maximum Amount ◽  
Reaction Products ◽  
Influence Of Temperature ◽  
Equilibrium Chemical ◽  
Program Data ◽  
Good Agreement

Detail investigation of equilibrium chemical reactions in WO3–H2O system using computer program FacktSage with the aim to establish influence of temperature and quantity of water on formation of compounds of H2WO4 and WO2(OH)2 as well as concomitant them compounds, evaporation products, decomposition and dissociation, that are contained in the program data base were carried out. Calculations in the temperature range from 100 to 3000 °С were carried out. The amount moles of water added to 1 mole of WO3 was varied from 0 to 27. It is found that the obtained data by the melting and evaporation temperatures of single-phase WO3 are in good agreement with the reference data and provide additionally detailed information on the composition of the gas phase. It was shown that under heating of 1 mole single-phase WO3 up to 3000 °С the predominant oxide that exist in gaseous phase is (WO3)2. Reactions of it formation from other oxides ((WO3)3 and (WO3)4) were proposed. It was established that compound H2WO4 is stable and it is decomposed on WO3 and H2O under 121 °C. Tungsten Oxide Hydrate WO2(OH)2 first appears under 400 °С and exists up to 3000 °С. Increasing quantity of Н2О in system leads to decreasing transition temperature of WO3 into both liquid and gaseous phases. It was established that adding to 1 mole WO3 26 mole H2O maximum amount (0,9044–0,9171 mole) WO2(OH)2 under temperatures 1400–1600 °С can be obtained, wherein the melting stage of WO3 is omitted. Obtained data also allowed to state that that from 121 till 400 °С WO3–Н2O the section in the О–W–H ternary system is partially quasi-binary because under these temperatures in the system only WO3 and Н2O are present. Under higher temperatures WO3–Н2O section becomes not quasi-binary since in the reaction products WO3 with Н2O except WO3 and Н2O, there are significant amounts of WO2(OH)2, (WO3)2, (WO3)3, (WO3)4 and a small amount of atoms and other compounds. Bibl. 12, Fig. 6, Tab. 5.

Explaining the magnetism of gold

2017 ◽  
Author(s):  
Robson de Farias
Keyword(s):  
Gas Phase ◽  
Computational Study ◽  
Formation Enthalpy ◽  
Gold Atom ◽  
Orbital Energy ◽  
Knudsen Effusion ◽  
Energy Diagram ◽  
Unpaired Electrons ◽  
The Difference ◽  
Good Agreement

<p>In the present work, a computational study is performed in order to clarify the possible magnetic nature of gold. For such purpose, gas phase Au<sub>2</sub> (zero charge) is modelled, in order to calculate its gas phase formation enthalpy. The calculated values were compared with the experimental value obtained by means of Knudsen effusion mass spectrometric studies [5]. Based on the obtained formation enthalpy values for Au<sub>2</sub>, the compound with two unpaired electrons is the most probable one. The calculated ionization energy of modelled Au<sub>2</sub> with two unpaired electrons is 8.94 eV and with zero unpaired electrons, 11.42 eV. The difference (11.42-8.94 = 2.48 eV = 239.29 kJmol<sup>-1</sup>), is in very good agreement with the experimental value of 226.2 ± 0.5 kJmol<sup>-1</sup> to the Au-Au bond<sup>7</sup>. So, as expected, in the specie with none unpaired electrons, the two 6s<sup>1</sup> (one of each gold atom) are paired, forming a chemical bond with bond order 1. On the other hand, in Au<sub>2</sub> with two unpaired electrons, the s-d hybridization prevails, because the relativistic contributions. A molecular orbital energy diagram for gas phase Au<sub>2</sub> is proposed, explaining its paramagnetism (and, by extension, the paramagnetism of gold clusters and nanoparticles).</p>

Temperature Dependence of the Air/Water Interface Revealed by Polarization Sensitive Sum-Frequency Generation Spectroscopy

2018 ◽  
Author(s):  
Daniel R. Moberg ◽  
Shelby C. Straight ◽  
Francesco Paesani
Keyword(s):  
Temperature Dependence ◽  
Low Frequency ◽  
Potential Energy Function ◽  
Md Simulations ◽  
Sum Frequency Generation ◽  
Water Molecules ◽  
Water Interface ◽  
Sum Frequency ◽  
Air Water Interface ◽  
Frequency Generation

<div> <div> <div> <p>The temperature dependence of the vibrational sum-frequency generation (vSFG) spectra of the the air/water interface is investigated using many-body molecular dynamics (MB-MD) simulations performed with the MB-pol potential energy function. The total vSFG spectra calculated for different polarization combinations are then analyzed in terms of molecular auto-correlation and cross-correlation contributions. To provide molecular-level insights into interfacial hydrogen-bonding topologies, which give rise to specific spectroscopic features, the vSFG spectra are further investigated by separating contributions associated with water molecules donating 0, 1, or 2 hydrogen bonds to neighboring water molecules. This analysis suggests that the low frequency shoulder of the free OH peak which appears at ∼3600 cm−1 is primarily due to intermolecular couplings between both singly and doubly hydrogen-bonded molecules. </p> </div> </div> </div>

Diffusion model for deposition of epitaxial GaAs layers prepared by the MOCVD method

1991 ◽  
Vol 56 (10) ◽  
pp. 2020-2029
Author(s):  
Jindřich Leitner ◽  
Petr Voňka ◽  
Josef Stejskal ◽  
Přemysl Klíma ◽  
Rudolf Hladina
Keyword(s):  
Experimental Data ◽  
Growth Rate ◽  
Kinetic Model ◽  
Gas Phase ◽  
Substrate Surface ◽  
Deposition Process ◽  
Hydrogen Atmosphere ◽  
Epitaxial Gaas ◽  
Kinetics Of ◽  
Good Agreement

The authors proposed and treated quantitatively a kinetic model for deposition of epitaxial GaAs layers prepared by reaction of trimethylgallium with arsine in hydrogen atmosphere. The transport of gallium to the surface of the substrate is considered as the controlling process. The influence of the rate of chemical reactions in the gas phase and on the substrate surface on the kinetics of the deposition process is neglected. The calculated dependence of the growth rate of the layers on the conditions of the deposition is in a good agreement with experimental data in the temperature range from 600 to 800°C.

scholarly journals Estimation of the Noise Source Level of a Commercial Ship Using On-Board Pressure Sensors

2021 ◽  
Vol 11 (3) ◽  
pp. 1243
Author(s):  
Hongseok Jeong ◽  
Jeung-Hoon Lee ◽  
Yong-Hyun Kim ◽  
Hanshin Seol
Keyword(s):  
Noise Source ◽  
Pressure Sensors ◽  
Low Frequency ◽  
Frequency Resolution ◽  
Source Strength ◽  
Recording Time ◽  
Source Level ◽  
The One ◽  
Hydrophone Array ◽  
Good Agreement

The dominant underwater noise source of a ship is known to be propeller cavitation. Recently, attempts have been made to quantify the source strength using on-board pressure sensors near the propeller, as this has advantages over conventional noise measurement. In this study, a beamforming method was used to estimate the source strength of a cavitating propeller. The method was validated against a model-scale measurement in a cavitation tunnel, which showed good agreement between the measured and estimated source levels. The method was also applied to a full-scale measurement, in which the source level was measured using an external hydrophone array. The estimated source level using the hull pressure sensors showed good agreement with the measured one above 400 Hz, which shows potential for noise monitoring using on-board sensors. A parametric study was carried out to check the practicality of the method. From the results, it was shown that a sufficient recording time is required to obtain a consistent level at high frequencies. Changing the frequency resolution had little effect on the result, as long as enough data were provided for the one-third octave band conversion. The number of sensors affected the mid- to low-frequency data.

DIELECTRIC CONSTANT AND SEEBECK COEFFICIENT FOR SEMICONDUCTORS: THERMODYNAMIC AND DFT STUDIES

2013 ◽  
Vol 12 (06) ◽  
pp. 1350057 ◽  
Author(s):  
HSIU-YA TASI ◽  
CHAOYUAN ZHU
Keyword(s):  
Boundary Condition ◽  
Dielectric Constant ◽  
Seebeck Coefficient ◽  
Gas Phase ◽  
Present Method ◽  
Dielectric Constants ◽  
Semiconductor Materials ◽  
Electronic Polarizability ◽  
Seebeck Coefficients ◽  
Good Agreement

Dielectric constants and Seebeck coefficients for semiconductor materials are studied by thermodynamic method plus ab initio quantum density functional theory (DFT). A single molecule which is formed in semiconductor material is treated in gas phase with molecular boundary condition and then electronic polarizability is directly calculated through Mulliken and atomic polar tensor (APT) density charges in the presence of the external electric field. This electronic polarizability can be converted to dielectric constant for solid material through the Clausius–Mossotti formula. Seebeck coefficient is first simulated in gas phase by thermodynamic method and then its value divided by its dielectric constant is regarded as Seebeck coefficient for solid materials. Furthermore, unit cell of semiconductor material is calculated with periodic boundary condition and its solid structure properties such as lattice constant and band gap are obtained. In this way, proper DFT function and basis set are selected to simulate electronic polarizability directly and Seebeck coefficient through chemical potential. Three semiconductor materials Mg 2 Si , β- FeSi 2 and SiGe are extensively tested by DFT method with B3LYP, BLYP and M05 functionals, and dielectric constants simulated by the present method are in good agreement with experimental values. Seebeck coefficients simulated by the present method are in reasonable good agreement with experiments and temperature dependence of Seebeck coefficients basically follows experimental results as well. The present method works much better than the conventional energy band structure theory for Seebeck coefficients of three semiconductors mentioned above. Simulation with periodic boundary condition can be generalized directly to treat with doped semiconductor in near future.

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