Charge distributions and chemical effects. XLV. Graphite

1988 ◽  
Vol 66 (10) ◽  
pp. 2631-2633 ◽  
Author(s):  
Andrea Peluso ◽  
Sándor Fliszár
Keyword(s):  
Heat Content ◽  
Zero Point ◽  
Van Der Waals Interactions ◽  
Bond Energies ◽  
Net Charge ◽  
Point Energy ◽  
Bond Forming ◽  
Experimental Heat ◽  
Chemical Effects ◽  
Debye Temperatures

The zero point energy of graphite, [Formula: see text], is deduced from Debye's theory by separating the lattice vibrations into two approximately independent parts, with Debye temperatures [Formula: see text] (in plane) and [Formula: see text] (perpendicular). A balanced evaluation gives [Formula: see text]. The bond energies of graphite in its potential minimum are derived from those of polynuclear benzenoїd hydrocarbons using a formula describing bond energies in terms of the charges at the bond-forming atoms. These energies plus a consideration of (i) van der Waals interactions between layers (~1.2 kcal mol−1), (ii) ZPE = 3.68, and (iii) the experimental heat content. HT − H0 = 0.25 kcal mol−1, lead to a theoretical enthalpy of atomization, ΔHa(298.15) = 174.6, which is ~2% larger than its experimental counterpart, 170.9 kcal mol−1. Exploiting the fact that the carbon atoms are electroneutral in graphite and not so in benzenoїd hydrocarbons, the results obtained for graphite support the approximate validity of bond energies deduced for polynuclear benzenoїd hydrocarbons and of the net charge, 14.8 × 10−3 e, deduced for the carbon atom of benzene.

scholarly journals Dynamical strengthening of covalent and non-covalent molecular interactions by nuclear quantum effects at finite temperature

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Huziel E. Sauceda ◽  
Valentin Vassilev-Galindo ◽  
Stefan Chmiela ◽  
Klaus-Robert Müller ◽  
Alexandre Tkatchenko
Keyword(s):  
Finite Temperature ◽  
Electrostatic Interactions ◽  
Zero Point ◽  
Quantum Effects ◽  
Van Der Waals Interactions ◽  
Interatomic Distances ◽  
Point Energy ◽  
Molecular Bond ◽  
Energy Surfaces ◽  
Nuclear Quantum Effects

AbstractNuclear quantum effects (NQE) tend to generate delocalized molecular dynamics due to the inclusion of the zero point energy and its coupling with the anharmonicities in interatomic interactions. Here, we present evidence that NQE often enhance electronic interactions and, in turn, can result in dynamical molecular stabilization at finite temperature. The underlying physical mechanism promoted by NQE depends on the particular interaction under consideration. First, the effective reduction of interatomic distances between functional groups within a molecule can enhance the n → π* interaction by increasing the overlap between molecular orbitals or by strengthening electrostatic interactions between neighboring charge densities. Second, NQE can localize methyl rotors by temporarily changing molecular bond orders and leading to the emergence of localized transient rotor states. Third, for noncovalent van der Waals interactions the strengthening comes from the increase of the polarizability given the expanded average interatomic distances induced by NQE. The implications of these boosted interactions include counterintuitive hydroxyl–hydroxyl bonding, hindered methyl rotor dynamics, and molecular stiffening which generates smoother free-energy surfaces. Our findings yield new insights into the versatile role of nuclear quantum fluctuations in molecules and materials.

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).

The thermal properties of alkali halide crystals II. Analysis of experimental results

1957 ◽  
Vol 242 (1231) ◽  
pp. 478-492 ◽  
Keyword(s):  
Sodium Chloride ◽  
Geometric Mean ◽  
Low Frequency ◽  
Zero Point ◽  
Crystalline Lattice ◽  
Zero Point Energy ◽  
Point Energy ◽  
Experimental Heat ◽  
Atomic Vibrations ◽  
Alkali Halide Crystals

The results reported in part I, together with similar results for sodium chloride, have been analyzed in terms of the spectrum of harmonic vibrations of the crystalline lattice; since the zero-point energy proves to be small, the analysis should conform fairly closely to that of a static lattice. ʘ 0 and the coefficients of the terms in v 2 , v 4 and v 6 in the low-frequency expansion of the spectrum have been derived from the data for the region T < ʘ D /20. The values of ʘ 0 agree well with ʘ (elastic) calculated from the elastic properties of the crystals. After correction for thermal expansion, the results in the temperature range immediately above ʘ D /6 yield ʘ ∞ and the first three even moments of the spectrum ( μ 2 , μ 4 , and μ 6 ) when fitted to the Thirring expansion for ʘ D . For the three potassium salts, and again for the two sodium salts, the ratio ʘ 0 /ʘ ∞ appears to depend almost entirely upon the mass ratio of the ions. Values of this ratio suggest that the type of interatomic force is determined primarily by the alkali ion. Negative moments of the spectrum, together with μ 1 and the geometric mean frequency v g , have been derived from integrals of the form ʃ F 0 ( C v / T s )d T , with an accuracy comparable to that of the primary experimental heat capacities. Explicit spectra have not been com­puted, but instead v g , Θ 0 and the μ n have all been correlated in a graph of the function v D (n) = {1/3( n + 3) μ n } 1/ n . Potassium bromide is used as an illustrative example. The sharp curvature of the function v D (n) for negative values of n indicates that moments for n < — 1 give critical information about the form of the spectrum. The zero-point energies of the crystals have been calculated from μ 1 and compared with values derived by the approximate method of Domb & Salter (1952). The estimated increase in the volume of the crystal caused by zero-point energy ranges from 0.23% for potassium iodide to 0.37% for sodium chloride. By subtracting the heat capacity given by the Thirring expansion we may estimate the effect of anharmonicity of the vibrations. This seems to be roughly determined by the ratio of the amplitude of atomic vibrations to the interatomic distance.

On the Use of Quantum Thermal Bath in Unimolecular Fragmentation Simulations

2019 ◽  
Author(s):  
Riccardo Spezia ◽  
Hichem Dammak
Keyword(s):  
Degrees Of Freedom ◽  
Molecular Simulations ◽  
Zero Point ◽  
Thermal Bath ◽  
Unimolecular Dissociation ◽  
Point Energy ◽  
Rotational Degrees Of Freedom ◽  
The Difference ◽  
Nuclear Effects

<div> <div> <div> <p>In the present work we have investigated the possibility of using the Quantum Thermal Bath (QTB) method in molecular simulations of unimolecular dissociation processes. Notably, QTB is aimed in introducing quantum nuclear effects with a com- putational time which is basically the same as in newtonian simulations. At this end we have considered the model fragmentation of CH4 for which an analytical function is present in the literature. Moreover, based on the same model a microcanonical algorithm which monitor zero-point energy of products, and eventually modifies tra- jectories, was recently proposed. We have thus compared classical and quantum rate constant with these different models. QTB seems to correctly reproduce some quantum features, in particular the difference between classical and quantum activation energies, making it a promising method to study unimolecular fragmentation of much complex systems with molecular simulations. The role of QTB thermostat on rotational degrees of freedom is also analyzed and discussed. </p> </div> </div> </div>

scholarly journals Modulation of optical absorption in m-Fe1−xRuxS2 and exploring stability in new m-RuS2

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
H. Joshi ◽  
M. Ram ◽  
N. Limbu ◽  
D. P. Rai ◽  
B. Thapa ◽  
...  
Keyword(s):  
Optical Absorption ◽  
Phonon Dispersion ◽  
Applied Pressure ◽  
Orthorhombic Phase ◽  
Zero Point ◽  
Computational Method ◽  
Crystal Field Theory ◽  
Point Energy ◽  
Practical Applications ◽  
New Phase

AbstractA first-principle computational method has been used to investigate the effects of Ru dopants on the electronic and optical absorption properties of marcasite FeS2. In addition, we have also revealed a new marcasite phase in RuS2, unlike most studied pyrite structures. The new phase has fulfilled all the necessary criteria of structural stability and its practical existence. The transition pressure of 8 GPa drives the structural change from pyrite to orthorhombic phase in RuS2. From the thermodynamical calculation, we have reported the stability of new-phase under various ranges of applied pressure and temperature. Further, from the results of phonon dispersion calculated at Zero Point Energy, pyrite structure exhibits ground state stability and the marcasite phase has all modes of frequencies positive. The newly proposed phase is a semiconductor with a band gap comparable to its pyrite counterpart but vary in optical absorption by around 106 cm−1. The various Ru doped structures have also shown similar optical absorption spectra in the same order of magnitude. We have used crystal field theory to explain high optical absorption which is due to the involvement of different electronic states in formation of electronic and optical band gaps. Lӧwdin charge analysis is used over the customarily Mulliken charges to predict 89% of covalence in the compound. Our results indicate the importance of new phase to enhance the efficiency of photovoltaic materials for practical applications.

scholarly journals Time-Resolved Measurements and Master Equation Modelling of the Unimolecular Decomposition of CH3OCH2

2020 ◽  
Vol 234 (7-9) ◽  
pp. 1233-1250 ◽  
Author(s):  
Arrke J. Eskola ◽  
Mark A. Blitz ◽  
Michael J. Pilling ◽  
Paul W. Seakins ◽  
Robin J. Shannon
Keyword(s):  
Energy Transfer ◽  
Master Equation ◽  
Rate Coefficient ◽  
Zero Point ◽  
Buffer Gas ◽  
Unimolecular Decomposition ◽  
Time Resolved ◽  
Point Energy ◽  
Wide Range ◽  
Transfer Parameters

AbstractThe rate coefficient for the unimolecular decomposition of CH3OCH2, k1, has been measured in time-resolved experiments by monitoring the HCHO product. CH3OCH2 was rapidly and cleanly generated by 248 nm excimer photolysis of oxalyl chloride, (ClCO)2, in an excess of CH3OCH3, and an excimer pumped dye laser tuned to 353.16 nm was used to probe HCHO via laser induced fluorescence. k1(T,p) was measured over the ranges: 573–673 K and 0.1–4.3 × 1018 molecule cm−3 with a helium bath gas. In addition, some experiments were carried out with nitrogen as the bath gas. Ab initio calculations on CH3OCH2 decomposition were carried out and a transition-state for decomposition to CH3 and H2CO was identified. This information was used in a master equation rate calculation, using the MESMER code, where the zero-point-energy corrected barrier to reaction, ΔE0,1, and the energy transfer parameters, ⟨ΔEdown⟩ × Tn, were the adjusted parameters to best fit the experimental data, with helium as the buffer gas. The data were combined with earlier measurements by Loucks and Laidler (Can J. Chem.1967, 45, 2767), with dimethyl ether as the third body, reinterpreted using current literature for the rate coefficient for recombination of CH3OCH2. This analysis returned ΔE0,1 = (112.3 ± 0.6) kJ mol−1, and leads to $k_{1}^{\infty}(T)=2.9\times{10^{12}}$ (T/300)2.5 exp(−106.8 kJ mol−1/RT). Using this model, limited experiments with nitrogen as the bath gas allowed N2 energy transfer parameters to be identified and then further MESMER simulations were carried out, where N2 was the buffer gas, to generate k1(T,p) over a wide range of conditions: 300–1000 K and N2 = 1012–1025 molecule cm−3. The resulting k1(T,p) has been parameterized using a Troe-expression, so that they can be readily be incorporated into combustion models. In addition, k1(T,p) has been parametrized using PLOG for the buffer gases, He, CH3OCH3 and N2.

VACUUM ENERGY IN SPHERICAL DOMAINS: WKB AND UNIFORM ASYMPTOTIC EXPANSIONS

1996 ◽  
Vol 11 (22) ◽  
pp. 4129-4146 ◽  
Author(s):  
AUGUST ROMEO
Keyword(s):  
Zeta Function ◽  
Asymptotic Expansions ◽  
Zero Point ◽  
Massless Scalar ◽  
Massless Scalar Field ◽  
Point Energy ◽  
Dimensional Dependence ◽  
Spherical Domains ◽  
Spectral Zeta Function ◽  
Uniform Asymptotic Expansions

We evaluate the finite part of the regularized zero-point energy for a massless scalar field confined in the interior of a D-dimensional spherical region. While some insight is offered into the dimensional dependence of the WKB approximations by examining the residues of the spectral-zeta-function poles, a mode-sum technique based on an integral representation of the Bessel spectral zeta function is applied with the help of uniform asymptotic expansions (u.a.e.’s).

scholarly journals An investigation into the existence of zero-point energy in the Rock-Salt Lattice by an X-Ray Diffraction Method

1928 ◽  
Vol 118 (779) ◽  
pp. 334-350 ◽  
Keyword(s):  
Rock Salt ◽  
Diffraction Method ◽  
Zero Point ◽  
Temperature Factor ◽  
X Rays ◽  
Zero Point Energy ◽  
Chlorine Atoms ◽  
Point Energy ◽  
X Ray ◽  
State Of Rest

In the present paper we shall attempt to collate the results of four separate lines of research which, taken together, appear to provide some interesting checks between theory and experiment. The investigations to be considered are (1) the discussion by Waller* and by Wentzel,† on the basis of the quantum (wave) mechanics, of the scattering of radiation by an atom ; (2) the calculation by Hartree of the Schrödinger distribution of charge in the atoms of chlorine and sodium ; (3) the measurements of James and Miss Firth‡ of the scattering power of the sodium and chlorine atoms in the rock-salt crystal for X-rays at a series of temperatures extending as low as the temperature of liquid air ; and (4) the theoretical discussion of the temperature factor of X-ray reflexion by Debye§ and by Waller.∥ Application of the laws of scattering to the distribution of charge calculated for the sodium and chlorine atoms, enables us to calculate the coherent atomic scattering for X-radiation, as a function of the angle of scattering and of the wave-length, for these atoms in a state of rest, assuming that the frequency of the X-radiation is higher than, and not too near the frequency of the K - absorption edge for the atom.¶ From the observed scattering power at the temperature of liquid air, and from the measured value of the temperature factor, we can, by applying the theory of the temperature effect, calculate the scattering power at the absolute zero, or rather for the atom reduced to a state of rest. The extrapolation to a state of rest will differ according to whether we assume the existence or absence of zero point energy in the crystal lattice. Hence we may hope, in the first place to test the agreement between the observed scattering power and that calculated from the atomic model, and in the second place to see whether the experimental results indicate the presence of zero-point energy or no.

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