STUDIES ON IONIC SOLVATION: PART III. NEW THEORY FOR CALCULATING HEATS OF HYDRATION OF MONOVALENT IONS AT 25 °C

1960 ◽  
Vol 38 (11) ◽  
pp. 2203-2216 ◽  
Author(s):  
A. M. Azzam
Keyword(s):  
Alkali Metals ◽  
Ionic Radius ◽  
Present Theory ◽  
Ionic Solvation ◽  
Positive Ions ◽  
Monovalent Ions ◽  
Ionic Size ◽  
Monovalent Ion ◽  
Experimental Values ◽  
Good Agreement

From Part I of this series, the structure of solution around a completely hydrated monovalent ion could be visualized. On the basis of this picture, the ionic heats of hydration is to be due to three terms. These three terms are critically discussed and evaluated for the case of alkali metals and halide ions.The present theory shows that the Born–Bjerrum term contributes a significant part to the heat and that the ionic radius value included in this term must be dependent only on the charge and not on the ionic size. The most probable value is 2.4 Å for the positive ions and 2.9 Å for the negative ions.The calculated ionic heats of hydration, which are in good agreement with the experimental values, are compared with those of previous theories.

THEORETICAL STUDIES ON SOLVATION: PART II. NEW THEORY FOR EVALUATION OF IONIC SOLVATION NUMBER FOR DIVALENT IONS AT 25 °C

1960 ◽  
Vol 38 (6) ◽  
pp. 993-1002 ◽  
Author(s):  
A. M. Azzam
Keyword(s):  
Present Theory ◽  
Water Molecules ◽  
Solvation Number ◽  
Divalent Ions ◽  
Ionic Solvation ◽  
Solvation Numbers ◽  
Aquo Complex ◽  
Solvent Molecules ◽  
Definition Of ◽  
Good Agreement

The concepts of ionic solvation are discussed and the definition of four types are suggested. Utilizing Webb's theory, values of the dielectric constant of water in terms of distance from a divalent ion are evaluated. The statistical mechanics of the distribution of solvent molecules round a divalent ion in aqueous solution has been worked out.The present theory shows that all divalent ions with radius less than 1.6 Å can have a saturated envelope of eight water molecules in excess of the Goldschmidt co-ordination number have to be accounted for as inner primary solvation number. The concept of catonium is suggested for such a stable aquo-complex entity. The catonium entity is further hydrated electrostatically in the normal way by primary and secondary solvation types. The conditions governing all types of solvation and their possible termination boundaries are discussed and evaluated.The theoretically calculated values of the ionic solvation numbers are in good agreement with the experimental results.

Systematic calculations of energy levels and transitions rates in Mo XXVIII

2020 ◽  
Vol 75 (8) ◽  
pp. 739-747
Author(s):  
Feng Hu ◽  
Yan Sun ◽  
Maofei Mei
Keyword(s):  
Energy Levels ◽  
Oscillator Strengths ◽  
Atomic Data ◽  
Data Sets ◽  
Electron Systems ◽  
Excitation Energies ◽  
Experimental Values ◽  
Qed Effects ◽  
Hyperfine Structures ◽  
Good Agreement

AbstractComplete and consistent atomic data, including excitation energies, lifetimes, wavelengths, hyperfine structures, Landé gJ-factors and E1, E2, M1, and M2 line strengths, oscillator strengths, transitions rates are reported for the low-lying 41 levels of Mo XXVIII, belonging to the n = 3 states (1s22s22p6)3s23p3, 3s3p4, and 3s23p23d. High-accuracy calculations have been performed as benchmarks in the request for accurate treatments of relativity, electron correlation, and quantum electrodynamic (QED) effects in multi-valence-electron systems. Comparisons are made between the present two data sets, as well as with the experimental results and the experimentally compiled energy values of the National Institute for Standards and Technology wherever available. The calculated values including core-valence correction are found to be in a good agreement with other theoretical and experimental values. The present results are accurate enough for identification and deblending of emission lines involving the n = 3 levels, and are also useful for modeling and diagnosing plasmas.

A DFT study of spherands containing five anisyl groups — Highly preorganized to bind the alkali metal

2006 ◽  
Vol 84 (8) ◽  
pp. 1045-1049 ◽  
Author(s):  
Shabaan AK Elroby ◽  
Kyu Hwan Lee ◽  
Seung Joo Cho ◽  
Alan Hinchliffe
Keyword(s):  
Density Functional Theory ◽  
Binding Energy ◽  
Density Functional ◽  
Ionic Radius ◽  
Binding Energies ◽  
Cavity Size ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray ◽  
Good Agreement

Although anisyl units are basically poor ligands for metal ions, the rigid placements of their oxygens during synthesis rather than during complexation are undoubtedly responsible for the enhanced binding and selectivity of the spherand. We used standard B3LYP/6-31G** (5d) density functional theory (DFT) to investigate the complexation between spherands containing five anisyl groups, with CH2–O–CH2 (2) and CH2–S–CH2 (3) units in an 18-membered macrocyclic ring, and the cationic guests (Li+, Na+, and K+). Our geometric structure results for spherands 1, 2, and 3 are in good agreement with the previously reported X-ray diffraction data. The absolute values of the binding energy of all the spherands are inversely proportional to the ionic radius of the guests. The results, taken as a whole, show that replacement of one anisyl group by CH2–O–CH2 (2) and CH2–S–CH2 (3) makes the cavity bigger and less preorganized. In addition, both the binding and specificity decrease for small ions. The spherands 2 and 3 appear beautifully preorganized to bind all guests, so it is not surprising that their binding energies are close to the parent spherand 1. Interestingly, there is a clear linear relation between the radius of the cavity and the binding energy (R2 = 0.999).Key words: spherands, preorganization, density functional theory, binding energy, cavity size.

scholarly journals DFT calculation and assignment of vibrational spectra of aryl and alkyl chlorophosphates

2014 ◽  
Vol 12 (2) ◽  
pp. 153-163
Author(s):  
Viktor Anishchenko ◽  
Vladimir Rybachenko ◽  
Konstantin Chotiy ◽  
Andrey Redko
Keyword(s):  
Vibrational Spectra ◽  
Basis Sets ◽  
Heavy Atoms ◽  
Wide Range ◽  
Complete Assignment ◽  
Key Factor ◽  
Polarization Functions ◽  
Experimental Values ◽  
Semi Empirical ◽  
Good Agreement

AbstractDFT calculations of vibrational spectra of chlorophosphates using wide range of basis sets and hybrid functionals were performed. Good agreement between calculated and experimental vibrational spectra was reached by the combination of non-empirical functional PBE0 with both middle and large basis sets. The frequencies of the stretching vibrations of the phosphate group calculated using semi-empirical functional B3LYP for all basis sets deviate significantly from the experimental values. The number of polarization functions on heavy atoms was shown to be a key factor for the calculation of vibrational frequencies of organophosphates. The importance of consideration of all the stable rotamers for a complete assignment of fundamental modes was shown.

scholarly journals Structural elastic and thermal properties of SrxCd1−x O mixed compounds — a theoretical approach

2014 ◽  
Vol 32 (3) ◽  
pp. 350-357
Author(s):  
Purvee Bhardwaj
Keyword(s):  
Phase Transition ◽  
Vibrational Energy ◽  
Zero Point ◽  
Study Phase ◽  
Energy Effect ◽  
Phase Transition Pressure ◽  
Vegard’S Law ◽  
Extended Interaction ◽  
Experimental Values ◽  
Good Agreement

AbstractIn the present paper, the structural and mechanical properties of alkaline earth oxides mixed compound SrxCd1−x O (0 ≤ x ≤ 1) under high pressure have been reported. An extended interaction potential (EIP) model, including the zero point vibrational energy effect, has been developed for this study. Phase transition pressures are associated with a sudden collapse in volume. Phase transition pressure and associated volume collapses [ΔV (Pt)/V(0)] calculated from this approach are in good agreement with the experimental values for the parent compounds (x = 0 and x = 1). The results for the mixed crystal counterparts are also in fair agreement with experimental data generated from the application of Vegard’s law to the data for the parent compounds.

The continuous absorption of light in alkali-metal vapours

1953 ◽  
Vol 219 (1136) ◽  
pp. 89-101 ◽  
Keyword(s):  
Cross Section ◽  
Alkali Metals ◽  
Theoretical Calculations ◽  
Wave Length ◽  
Energy Difference ◽  
Continuous Absorption ◽  
Absorption Of Light ◽  
Sodium Vapour ◽  
Good Agreement ◽  
Dipole Length

The first section of this paper is an account of some experiments on the absorption of light in sodium vapour from the series limit at 2412 Å to about 1600 Å (an energy difference of 2·6 eV). The absorption cross-section at the limit is 11·6 ± 1·2 x 10 -20 cm 2 . The cross-section decreases giving a minimum of 1·3 ± 0·6 x 10 -20 cm 2 at 1900 Å and then increases to 1600 Å. A theoretical calculation by Seaton based on the dipole-length formula gives good agreement with the experiments at the series limit and also correctly predicts the wave-length for the minimum, but it predicts a significantly lower absorption at the minimum. The experiments described in the first section of the paper conclude a series on the absorption of light in the alkali metals. The second section consists of a general discussion of the results of these experiments and of their relation to theoretical calculations. There is good agreement between theory and experiment except in regard to the magnitude of the absorption at the minimum.

The Thermodynamics Calculation of Mg-Zn Alloy

2007 ◽  
Vol 546-549 ◽  
pp. 447-450
Author(s):  
Tian Mo Liu ◽  
Hong Yi Zhou ◽  
Fu Sheng Pan
Keyword(s):  
Excess Entropy ◽  
Formation Enthalpy ◽  
Miedema Model ◽  
Activity Curve ◽  
Calculation Results ◽  
Experimental Values ◽  
Zn Alloy ◽  
Zn Alloys ◽  
Good Agreement

In the present work Miedema model has been developed, and the formation enthalpy of Mg-Zn alloys and the activity curve of Zn in Mg-Zn alloy at 1000K have been calculated according to the Miedema model. The calculation results showed that the formation enthalpy of Mg-Zn was small, and the excess entropy attributes a lot to the result. When excess enthopy was considered, the calculation results were found to be in good agreement with the experimental values.

Competitive reactions in the irradiation of anthracene + cyclohexane solutions

1959 ◽  
Vol 249 (1256) ◽  
pp. 51-64 ◽  
Keyword(s):  
Radiation Intensity ◽  
Quantitative Agreement ◽  
Radical Scavenger ◽  
Organic Systems ◽  
Low Concentrations ◽  
Radiation Induced ◽  
Experimental Values ◽  
Very High ◽  
Intensity Radiation ◽  
Good Agreement

Anthracene acts as a radical scavenger when present at low concentrations in irradiated hydrocarbons. A study has been made of the effect of radiation intensity and anthracene concentration on G( — A) , the number of anthracene molecules lost per 100 eV of energy absorbed. A theoretical calculation is made of the dependence of G( — A) on radiation intensity 1 and anthracene concentration ( A ), assuming that radiation-induced radicals (R.) are formed at random, and can either disappear by direct combination with one another, or with the anthracene to give RAR or RAAR bridges, or possibly some form of stabilized RA molecules. This theory is in good agreement with the experimental values of G( — A) measured at various low radiation intensities and anthracene concentrations. From the comparison estimates of the reactivity constants are derived. With very high intensity radiation quantitative agreement is less satisfactory, due to the non-steady conditions prevailing in a pulsed beam. The results obtained are compared with previous work on anthracene + hexane and iodine + cyclo hexane mixtures, in which the effect of radiation intensity was not investigated. The results reported here are of interest to the study of reaction kinetics in irradiated organic systems.

scholarly journals Design, Synthesis, Spectral and Theoretical Studies of Some Picrates

2019 ◽  
Vol 32 (1) ◽  
pp. 174-182
Author(s):  
S. Amala ◽  
G. Rajarajan ◽  
E. Dhineshkumar ◽  
M. Arockia doss ◽  
V. Thanikachalam
Keyword(s):  
Geometrical Parameters ◽  
Slight Effect ◽  
Design Synthesis ◽  
1H And 13C Nmr ◽  
Visible Spectra ◽  
Ft Ir ◽  
Uv Visible ◽  
Small Change ◽  
Experimental Values ◽  
Good Agreement

The structures of newly synthesized compounds (1-3) viz. 3-ethyl-5-methyl-2,6-bis(4- chlorophenyl)piperidin-1-ium picrate (1), 3-ethyl-5-methyl-2,6-bis(4-methylphenyl)piperidin-1-ium picrate (2) and 3-ethyl-5-methyl-2,6-bis(3,4-dimethoxyphenyl)piperidin-1-ium picrate (3) were confirmed by elemental analysis, FT-IR, 1H and 13C NMR. The UV-visible spectra, fluoresence, emission properties of synthesized 1-3 in different solvents were studied. Compounds 1-3 solvatochromic displays a slight effect of the emission and absorption spectrum, indicating a small change in the dipole moment upon excitation of compounds 1-3. All the compounds were investigated by DFT. The theoretical geometrical parameters are in good agreement with experimental values.

scholarly journals Current Status and Developments of the Atomic Database on Rare-Earths at Mons University (DREAM)

Atoms ◽  
2020 ◽  
Vol 8 (2) ◽  
pp. 18 ◽  
Author(s):  
Pascal Quinet ◽  
Patrick Palmeri
Keyword(s):  
Rare Earths ◽  
Spectral Lines ◽  
Oscillator Strengths ◽  
Current Status ◽  
Time Resolved ◽  
Hartree Fock ◽  
Lanthanide Atoms ◽  
Experimental Values ◽  
Theoretical Results ◽  
Good Agreement

The main purpose of the Database on Rare Earths At Mons University (DREAM) is to provide the scientific community with updated spectroscopic parameters related to lanthanide atoms (Z = 57–71) in their lowest ionization stages. The radiative parameters (oscillator strengths and transitions probabilities) listed in the database have been obtained over the past 20 years by the Atomic Physics and Astrophysics group of Mons University, Belgium, thanks to a systematic and extensive use of the pseudo-relativistic Hartree-Fock (HFR) method modified for taking core-polarization and core-penetration effects into account. Most of these theoretical results have been validated by the good agreement obtained when comparing computed radiative lifetimes and accurate experimental values measured by the time-resolved laser-induced fluorescence technique. In the present paper, we report on the current status and developments of the database that gathers radiative parameters for more than 72,000 spectral lines in neutral, singly-, doubly-, and triply-ionized lanthanides.

Sign in / Sign up

Export Citation Format

Share Document