Charge distributions and chemical effects. XXIV. On the role of vibrational energies in determining molecular stabilities

1981 ◽  
Vol 59 (9) ◽  
pp. 1381-1387 ◽  
Author(s):  
Sándor Fliszár ◽  
J.-L. Cantara
Keyword(s):  
Conformational Changes ◽  
Vibrational Energy ◽  
Heat Content ◽  
Zero Point ◽  
Enthalpies Of Formation ◽  
Chemical Binding ◽  
Nuclear Magnetic Resonance Spectra ◽  
Molecular Stability ◽  
Coulomb Type ◽  
Vibrational Energies

A simple equation has been derived for calculating accurate ZPE + HT − H0 (zero-point and heat content) energies of saturated hydrocarbons from their enthalpies of formation and carbon-13 nuclear magnetic resonance spectra. Applications to conformational analysis indicate a near invariance of vibrational energies with respect to chair–boat conformational changes of the cyclohexane ring, the loss in molecular stability arising then from a weakening of the chemical binding due to a reorganization of the electronic charges. The origin of the destabilizing effect of butane gauche interactions is found, in the cyclohexane series, in a weakening of the chemical binding (∼1.85 kcal/mol) which is partially compensated by a lowering (∼0.85 kcal/mol) vibrational energy, thus offering an explanation for the loss in molecular stability of ∼1.00 kcal/mol for one gauche interaction without invoking Coulomb-type repulsions between non-bonded atoms. Calculated enthalpies of formation are presentd for a number of cycloalkanes.

Charge distributions and chemical effects. XXXI. Molecular energies of ethylenic compounds

1983 ◽  
Vol 61 (1) ◽  
pp. 197-205 ◽  
Author(s):  
M.-T. Béraldin ◽  
S. Fliszâr
Keyword(s):  
Zero Point ◽  
Enthalpies Of Formation ◽  
Average Deviation ◽  
Bond Forming ◽  
Chemical Effects ◽  
Nuclear Magnetic Resonance Spectra ◽  
Energy Formula ◽  
Standard Enthalpies Of Formation ◽  
Vibrational Energies ◽  
Proper Consideration

The energy formula describing bond contributions in terms of the charges carried by the bond-forming atoms is applied to ethylenic compounds. It is shown in what manner σ and π electrons can be treated within the framework of the bond energy theory giving the atomization energy of the vibrationless molecule at 0 K. Proper consideration of zero-point and thermal vibrational energies leads to standard enthalpies of formation. These calculations, which are carried out on the basis of, 13C nuclear magnetic resonance spectra, agree with their experimental counterparts, within experimental uncertainties (~0.3 kcal mol−1 average deviation).

scholarly journals Charge distributions and chemical effects. XXIX. On the vibrational energies of chair and boat cyclohexane

1982 ◽  
Vol 60 (11) ◽  
pp. 1347-1351 ◽  
Author(s):  
J. P. Huvenne ◽  
G. Vergoten ◽  
G. Fleury ◽  
S. Odiot ◽  
S. Fliszár
Keyword(s):  
Force Field ◽  
Conformational Changes ◽  
Vibrational Energy ◽  
Zero Point ◽  
Local Symmetry ◽  
Cyclohexane Ring ◽  
Force Field Calculations ◽  
Similar Nature ◽  
Chemical Effects ◽  
Vibrational Energies

Local symmetry force field calculations are presented for the chair and boat forms of cyclohexane and the assignments of frequencies are given. The calculated zero-point and thermal vibrational energies indicate a near invariance of total vibrational energy with respect to chair–boat conformational changes of the cyclohexane ring, thus confirming results of similar nature derived from earlier theoretical thermochemical analyses.

scholarly journals Thermodynamics and Intermolecular Interactions of Nicotinamide in Neat and Binary Solutions: Experimental Measurements and COSMO-RS Concentration Dependent Reactions Investigations

2021 ◽  
Vol 22 (14) ◽  
pp. 7365
Author(s):  
Piotr Cysewski ◽  
Maciej Przybyłek ◽  
Anna Kowalska ◽  
Natalia Tymorek
Keyword(s):  
Intermolecular Interactions ◽  
Vibrational Energy ◽  
Perfect Match ◽  
Zero Point ◽  
Heat Capacity Change ◽  
Free Energies ◽  
Temperature Dependent ◽  
Scanning Calorimetry ◽  
Capacity Change ◽  
Self Association

In this study, the temperature-dependent solubility of nicotinamide (niacin) was measured in six neat solvents and five aqueous-organic binary mixtures (methanol, 1,4-dioxane, acetonitrile, DMSO and DMF). It was discovered that the selected set of organic solvents offer all sorts of solvent effects, including co-solvent, synergistic, and anti-solvent features, enabling flexible tuning of niacin solubility. In addition, differential scanning calorimetry was used to characterize the fusion thermodynamics of nicotinamide. In particular, the heat capacity change upon melting was measured. The experimental data were interpreted by means of COSMO-RS-DARE (conductor-like screening model for realistic solvation–dimerization, aggregation, and reaction extension) for concentration dependent reactions. The solute–solute and solute–solvent intermolecular interactions were found to be significant in all of the studied systems, which was proven by the computed mutual affinity of the components at the saturated conditions. The values of the Gibbs free energies of pair formation were derived at an advanced level of theory (MP2), including corrections for electron correlation and zero point vibrational energy (ZPE). In all of the studied systems the self-association of nicotinamide was found to be a predominant intermolecular complex, irrespective of the temperature and composition of the binary system. The application of the COSMO-RS-DARE approach led to a perfect match between the computed and measured solubility data, by optimizing the parameter of intermolecular interactions.

VIBRATIONAL ENERGIES OF MEMBERS IN STRUCTURAL NETWORKS FITTED WITH TUNED VIBRATION ABSORBERS

2006 ◽  
Vol 06 (02) ◽  
pp. 269-284 ◽  
Author(s):  
SUNNY K. GEORGE ◽  
K. SHANKAR
Keyword(s):  
Energy Level ◽  
Vibrational Energy ◽  
General Structure ◽  
Energy Levels ◽  
Complex Structure ◽  
Input Power ◽  
Vibration Absorbers ◽  
Tuned Vibration Absorbers ◽  
Vibrational Energies ◽  
Structural Networks

The distribution of vibrational energy in members of a complex structure with tuned absorbers attached at the joints and subjected to dynamic loading is studied. The concept of power flows through the structure is used to determine the time-averaged energy levels of each member in the structure. The power flows are calculated using the time-averaged product of force and velocity at the input and coupling points (joints) of a general structure made of axially vibrating rods. The receptance approach is used to calculate the coupling forces and velocities in the structure. By balancing the input power against the dissipated powers, the time-averaged energy levels in members are determined. The main criteria studied here is the reduction in the frequency-averaged vibrational energy level of a member when an absorber is attached, expressed as a percentage compared to the case where there are no absorbers. The concept is first illustrated with a simple model of 2 axially vibrating rods with an absorber attached to the joint. Next, a more complex structure comprising 8 rods with arbitrary orientations and several absorbers attached to junctions is studied. The effect of activating absorbers at various locations on reducing the energy levels of certain members is examined. It is possible to estimate the usefulness of the absorber with respect to any member by determining the percentage reduction of energy level for that member.

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.

ON THE NECKING-IN PROCESS IN CLUSTER DECAYS

1990 ◽  
Vol 05 (20) ◽  
pp. 3901-3928 ◽  
Author(s):  
K. DEPTA ◽  
J. A. MARUHN ◽  
HOU-JI WANG ◽  
A. SĂNDULESCU ◽  
W. GREINER ◽  
...  
Keyword(s):  
Potential Energy Surfaces ◽  
Vibrational Energy ◽  
Correction Term ◽  
Zero Point ◽  
Alpha Decay ◽  
Shell Correction ◽  
Macroscopic Models ◽  
Excellent Description ◽  
Energy Surfaces ◽  
Zero Point Vibrational Energy

Two new macroscopic models (liquid drop and Yukawa-plus-exponential) describing the decays with emission of large fragments including alpha decay are developed. The proposed shape parametrization consists of two intersecting spheres smoothly joined by a third "rolling sphere". The first two spheres describe asymptotically the charge and mass asymmetries and the third one the necking-in process. It is shown that the potential energy surfaces in the neck and the relative distance between the centers of the spheres (for a given mass and charge fragmentation) lead to different dynamical paths depending on the mass and charge of the emitted fragment. Along the path a phenomenological shell correction term and a zero point vibrational energy are introduced. It is shown that this model gives an excellent description of the present experimental data.

Diatomic molecules energy spectra for the generalized Mobius square potential model

2020 ◽  
Vol 34 (21) ◽  
pp. 2050209
Author(s):  
U. S. Okorie ◽  
A. N. Ikot ◽  
M. U. Ibezim-Ezeani ◽  
Hewa Y. Abdullah
Keyword(s):  
Dissociation Energy ◽  
Approximation Scheme ◽  
Potential Model ◽  
Vibrational Energy ◽  
Diatomic Molecules ◽  
Energy Spectra ◽  
Equilibrium Bond Length ◽  
Quantum Numbers ◽  
Vibrational Energies ◽  
Potential Parameters

The modified version of the generalized Mobius square (GMS) potential has been obtained by employing the dissociation energy and equilibrium bond length as explicit parameters. The potential parameters have been defined in terms of the molecular parameters. The modified GMS potential has also been used to model internuclear interaction potential curves for different states of diatomic molecules. Also, we have obtained the rotational–vibrational energy spectra of the new GMS potential model, both analytically and numerically for the different diatomic molecules. This was done by employing a Pekeris-type approximation scheme and an appropriate coordinate transformation to solve the Schrodinger equation. Our results have been compared with the experimental Rydberg–Klein–Rees (RKR) data and its corresponding average absolute deviations in terms of the dissociation energy computed. The effects of the vibrational and rotational quantum numbers on the rotational–vibrational energies for the different states of the various diatomic molecules have also been discussed. This paper has shown to be highly relevant to the studies of thermodynamic and thermochemical functions of diatomic molecules.

VIBRATING NEUTRON STARS

1967 ◽  
Vol 45 (9) ◽  
pp. 2823-2831 ◽  
Author(s):  
Carl J. Hansen ◽  
Sachiko Tsuruta
Keyword(s):  
Neutron Stars ◽  
Storage Capacity ◽  
Vibrational Energy ◽  
Crab Nebula ◽  
X Rays ◽  
Vibrational Heating ◽  
Large Spread ◽  
Vibrational Energies ◽  
The Crab Nebula ◽  
Urca Process

The time variation of some interesting properties of vibrating neutron stars is considered. The models used are based on two nuclear potentials that cover a large spread of possibilities. The modified URCA neutrino process has been assumed to be the major damping mechanism. The calculations are performed both for the case when the vibration energy is partially converted into heat through the URCA process and for the case when this conversion does not take place. It is found that the vibrational energy-storage capacity is extremely model-dependent. The vibrational energies at 1 000 years range from about 1047 to 1050 ergs, which are sufficiently large as a possible energy source for the X rays from the Crab Nebula, ft is shown also that the cooling times of neutron stars will not be significantly increased by the inclusion of the vibrational heating.

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