Ab initio molecular orbital calculations on the transition state for the addition of a methyl radical to vinyl monomers

Ab initio molecular orbital calculations have been performed on the transition state for the addition of methyl radical to twelve vinyl monomers using the SV 3–21G basis set. A linear relationship has been found between the calculated energies of activation and previously calculated energies of reaction. This supports the assumption of an Evans-Polanyi type rule in previous work which attempted to correlate reactivity with calculated energies of reaction. The activation energies obtained for methyl addition to butadiene and styrene were calculated to be negative. This is caused by errors introduced by a number of sources, viz. basis set superposition error, spin contamination and zero point energy. These errors are discussed. Previous authors have reported reasonable agreement between calculated activation energies at SV3–21G and experimental values for methyl addition to ethylene, this work suggests that this agreement was coincidental and results from the fortuitous cancellation of errors. The nature of the transition state for these radical addition reactions is discussed and the limitations of the SV3–21G basis set are highlighted. The theoretical prediction of activation energies for radical addition reactions would require much larger calculations, beyond the computational means of most research laboratories.     

Highly Accurate CCSD(T) and DFT–SAPT Stabilization Energies of H‐Bonded and Stacked Structures of the Uracil Dimer

The CCSD(T) interaction energies for the H‐bonded and stacked structures of the uracil dimer are determined at the aug‐cc‐pVDZ and aug‐cc‐pVTZ levels. On the basis of these calculations we can construct the CCSD(T) interaction energies at the complete basis set (CBS) limit. The most accurate energies, based either on direct extrapolation of the CCSD(T) correlation energies obtained with the aug‐cc‐pVDZ and aug‐cc‐pVTZ basis sets or on the sum of extrapolated MP2 interaction energies (from aug‐cc‐pVTZ and aug‐cc‐pVQZ basis sets) and extrapolated ΔCCSD(T) correction terms [difference between CCSD(T) and MP2 interaction energies] differ only slightly, which demonstrates the reliability and robustness of both techniques. The latter values, which represent new standards for the H‐bonding and stacking structures of the uracil dimer, differ from the previously published data for the S22 set by a small amount. This suggests that interaction energies of the S22 set are generated with chemical accuracy. The most accurate CCSD(T)/CBS interaction energies are compared with interaction energies obtained from various computational procedures, namely the SCS–MP2 (SCS: spin‐component‐scaled), SCS(MI)–MP2 (MI: molecular interaction), MP3, dispersion‐augmented DFT (DFT–D), M06–2X, and DFT–SAPT (SAPT: symmetry‐adapted perturbation theory) methods. Among these techniques, the best results are obtained with the SCS(MI)–MP2 method. Remarkably good binding energies are also obtained with the DFT–SAPT method. Both DFT techniques tested yield similarly good interaction energies. The large magnitude of the stacking energy for the uracil dimer, compared to that of the benzene dimer, is explained by attractive electrostatic interactions present in the stacked uracil dimer. These interactions force both subsystems to approach each other and the dispersion energy benefits from a shorter intersystem separation.     

Dyson-corrected orbital energies for the perturbative treatment of electron correlation

The effect of replacing the Hartree–Fock one-particle energies with ionization potentials obtained from inverse Dyson equation when calculating electron correlation energies perturbatively is investigated. Though the energy shifts vary from system to system, the slight decrease of the resulting excitation energies at around equilibrium geometries leads to a slight increase of the correlation energies in most cases. In the dissociation limit the inverse Dyson equation opens the gap, thus nondiverging potential curves emerge even at the restricted Hartree–Fock (RHF)+RS2 level. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 713–719, 1998     

Geometry,basis set,and correlation energy dependence of computed protonation energies of imino bases

The nitrogen protonation energies of the imino bases HN?CHR, where R is H, CH₃, NH₂, OH, and F, have been evaluated to determine the dependence of absolute and relative protonation energies on geometry, basis set, and correlation effects. Reliable absolute protonation energies require a basis set larger than a split-valence plus polarization basis, the inclusion of correlation, and optimized geometries of at least Hartree–Fock 4-31G quality. Consistent relative protonation energies can be obtained at the Hartree–Fock level with smaller basis sets. Extending the split-valence basis set by the addition of polarization functions on all atoms decreases the computed absolute Hartree–Fock nitrogen protonation energies of the imino bases HN?CHR except when R is F, but increases the oxygen protonation energies of the carbonyl bases O?CHR.     

Tseng's calculations of low energy pair production

We review the theoretical work 1971–1997 of H.K. Tseng on low energy pair production. In this work numerical calculations were performed in independent particle approximation in a screened self-consistent central potential, expanding the S-matrix element in partial waves and multipoles. Sampling techniques in partial waves and multipoles were used to extend the calculations to higher energies (up to 10 Mev). Total cross sections, the positron energy spectrum, the positron angular distributions, and the positron–photon polarization correlations were studied. Agreement was obtained with most experiments, although some anomalies remained at the lowest energies (particularly at 1082 keV). Atomic screening of the nuclear charge decreases cross sections at higher energies, as described by a form factor in the momentum transfer to the nucleus. In an intermediate energy regime point Coulomb results in a shifted energy spectrum may be used. At low energies screening increases cross sections, and this is characterized in terms of a normalization screening factor which describes the change in magnitude of electron and positron wave functions at small distances. In this low energy regime angular distribution shapes and polarization correlations are independent of screening.     

The tautomers of uracil: A local correlation treatment

The relative energies of all six uracil tautomers have been determined at the MP 4(SDQ )/6-31G** level, using both conventional correlation theory and the Local Correlation method. Geometries were optimized at the SCF /6-31G* level with offset forces. Comparison of our energies with energies from structures optimized at the SCF level supports the conclusion that offset forces are an advantageous alternative to correlated geometry optimization. The Local Correlation method compares very well with conventional Møller–Plesset theory, recovering at least 98.4% of the conventional correlated energy in all cases. More importantly, the relative energies also show good agreement with the conventional results, even for these delocalized systems. CPU timings show a substantial computational savings for the Local Correlation method over the conventional method. The results of the local method using Boys localization are compared with those using Pipek–Mezey localization. The dioxo tautomer ( 1 ) is predicted to be the most stable. The ( 1 )–( 3 ) and ( 1 )–( 4 ) energy differences are found to be within the bounds estimated from experimental work. © 1993 John Wiley & Sons, Inc.     

C?H Bond dissociation of acetylene: Local density functional calculations

The C? H bond dissociation energy of acetylene was computed by both ab initio approaches and density functional theory in a local density approximation (DFT–LDA ). Structures and energies for acetylene and its dissociation products (the ethynyl and hydrogen radicals) are presented and compared. Using directly computed HCCH and HCC· energies and the exact H· value, the DFT–LDA calculations are found to yield C? H dissociation energies ranging from 129 to 131 kcal/mol, in good agreement with recent experimental and the highest level theoretical results. The DFT–LDA results show little dependence upon the computational procedure used to obtain geometries.     

Evaluation of density functional theory in the bond rupture of octane

Density functional methods at the 6-31G* level are applied to the rupture of n-octane into methyl–heptyl, ethyl–hexyl, propyl–pentyl, and butyl–butyl radical fragments. The energetics of the radicals at UMP3, UMP2/6-31G*//UHF/6-31G* (hereafter referred to as UMP), are compared to UB3LYP/6-31G* results (referred to as UB). Although the UMP approach matches additivity energies to within 5 kcal/mol, it fails to mimic the overall energetic trend. The UB energies agree with additivity estimates and trends to within 1–2 kcal/mol and radical entropies deviate by only 2 e.u. from available experimental data. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 154–167, 1998     

Computational insight into asymmetric uranyl-salophen coordinated with cyclohexenone derivatives

Uranyl–salophen (U–S) complexes, as modified by unilateral benzene and coordinated with cyclohexenones substituted by methyls or fluorines in E/Z-types, were investigated using density functional theory calculations at the level of B3LYP/6–311G** basis set. The results indicated that the O of substituted cyclohexenones could coordinate with U of the asymmetric U–S complexes. When the C=C bond of cyclohexenones was located upward in the twisted salophen plane, the binding energies of the cyclohexenones to the asymmetric U–S and Wiberg bond indices (WBIs) of carbonyl oxygen to uranium (U–O) were higher than those of the C=C bonds located downward. It could be concluded that when cyclohexenones were coordinated to the asymmetric U–S, the major products would be the complexes in which the C=C bond of cyclohexenones locates upward in the configuration. Binding energies of the E-type substituted cyclohexenones to the asymmetric U–S were higher than those for the Z-type ones.     

Physicochemical characterization of α‐chitin, β‐chitin,and γ‐chitin separated from natural resources

We isolated α‐chitin, β‐chitin, and γ‐chitin from natural resources by a chemical method to investigate the crystalline structure of chitin. Its characteristics were identified with Fourier transform infrared (FTIR) and solid‐state cross‐polarization/magic‐angle‐spinning (CP–MAS) ¹³C NMR spectrophotometers. The average molecular weights of α‐chitin, β‐chitin, and γ‐chitin, calculated with the relative viscosity, were about 701, 612, and 524 kDa, respectively. In the FTIR spectra, α‐chitin, β‐chitin, and γ‐chitin showed a doublet, a singlet, and a semidoublet at the amide I band, respectively. The solid‐state CP–MAS ¹³C NMR spectra revealed that α‐chitin was sharply resolved around 73 and 75 ppm and that β‐chitin had a singlet around 74 ppm. For γ‐chitin, two signals appeared around 73 and 75 ppm. From the X‐ray diffraction results, α‐chitin was observed to have four crystalline reflections at 9.6, 19.6, 21.1, and 23.7 by the crystalline structure. Also, β‐chitin was observed to have two crystalline reflections at 9.1 and 20.3 by the crystalline structure. γ‐Chitin, having an antiparallel and parallel structure, was similar in its X‐ray diffraction patterns to α‐chitin. The exothermic peaks of α‐chitin, β‐chitin, and γ‐chitin appeared at 330, 230, and 310, respectively. The thermal decomposition activation energies of α‐chitin, β‐chitin, and γ‐chitin, calculated by thermogravimetric analysis, were 60.56, 58.16, and 59.26 kJ mol^?1, respectively. With the Arrhenius law, ln β was plotted against the reciprocal of the maximum decomposition temperature as a straight line; there was a large slope for large activation energies and a small slope for small activation energies. α‐Chitin with high activation energies was very temperature‐sensitive; β‐Chitin with low activation energies was relatively temperature‐insensitive. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3423–3432, 2004     

Quantum chemical comparison of vertical,adiabatic, and 0‐0 excitation energies: The PYP and GFP chromophores

A number of benchmark studies investigating the performance of quantum chemical methods for calculating vertical excitation energies are today available in the literature. However, less established is the variation between methods in their estimates of the differences between vertical, adiabatic, and 0‐0 excitation energies. To this end, such excitation energies are here calculated for the bright S₁ states of the anionic chromophores of the photoactive yellow protein (PYP) and the green fluorescent protein (GFP) in the gas phase using configuration interaction singles, complete active space self‐consistent field, coupled‐cluster singles and doubles, and time‐dependent density functional theory methods. Although the estimates of the excitation energies vary by more than 1 eV between the methods, the differences between the different types of excitation energies are found to be relatively method‐insensitive, varying by ～0.1 eV only for these particular chromophores. Specifically, the adiabatic energies are uniformly 0.10–0.17 (PYP) and 0.06–0.17 eV (GFP) lower than the vertical energies, and the 0‐0 energies are similarly 0.09–0.14 (PYP) and 0.07–0.17 eV (GFP) lower than the adiabatic energies. © 2012 Wiley Periodicals, Inc.     

Some properties of intermediate regions in interpenetrating polymeric networks

The molecular mobility in an interpenetrating polymeric network (IPN) based on crosslinked polyurethane (1) and styrene–divinylbenzene copolymer (2) was studied by broad-line NMR spectroscopy and reversed gas chromatography. NMR and infrared investigations show the absence of chemical interaction between the two constituent networks. For an IPN in the temperature range ?196 to 120°C transition regions corresponding to the individual networks and to an intermediate region were found, the latter being characterized by an additional transition at 25–60°C (NMR spectroscopy) and 44–78°C (gas chromatography). The existence of an intermediate region, presumably of loosely packed structure, leads to a shift in the beginning of the temperature transition in IPN to lower temperature and to a decrease in activation energies of relaxation in comparison with the individual networks. The activation energies in IPN are decreased with increasing weight fraction of the second network.     

负载金催化剂上CO氧化反应活性与金属氧化物载体中金属-氧结合能之间的关系

讨论了金属氧化物载体(MOx)对其负载纳米金催化剂(Au/MOx)上CO氧化反应的影响。采用典型的共沉淀法和沉积-沉淀法在完全相同的焙烧条件下制备了一系列MOx负载金催化剂,以CO氧化转化50%时的反应温度(T1/2)定量评价了MOx载体和Au/MOx催化剂的催化活性。进一步将MOx载体与相应Au/MOx催化剂的T1/2值之差对MOx载体的金属-氧结合能做曲线进行关联,发现二者呈明显的火山型关系。这一结果表明,采用具有适当金属-氧结合能(300–500 atom O)的MOx可大大提高沉积于其上的Au纳米颗粒的催化活性。     

Effect of composition on the thermal behavior of NiMnGa alloys

The methods to determine martensitic transformation temperature, enthalpy and entropy change, specific heat capacity change with temperature, and transformation activation energies of Ni–%29.5Mn–%21Ga, Ni–%29Mn–%21Ga, Ni–%29.5Mn–%20Ga, and Ni–%28.5Mn–%20.5Ga (atomic percentage) alloys were investigated by differential scanning calorimetry. It was observed that the transformation temperature increased with an increase in atomic nickel ratio. Meanwhile, it was detected that the change in enthalpy increases with the amount of nickel. The highest values of entropy change and the heat capacity at room temperature were observed in the alloy having the least amount of nickel in it.     

Computer simulation to investigate absorption of energies of arrayed disk‐like nanoiron particles under magnetic fields

In this research, we focus on the studying of absorbed energies of materials under an external magnetic field frequency of 0.5 GHz. This wave corresponds to microwave irradiation. The absorbent materials were arrayed disk‐like iron particles with dimension on the nanometer scale and magnetic responses of the particles were simulated by solving the Landau–Lifshitz–Gilbert equation. The external fields were applied from various directions and energies of absorption of the system were calculated. The maximum absorbed energies were found when the field was 135° ± 30° along the X‐axis or the Y‐axis. The current simulation demonstrated that the direction of applied field results in different absorption energies of the system.     

Theoretical study on the isomerization and tautomerism in barbituric acid

Isomerization and tautomerism of 16 isomers of barbituric acid (BA) were studied at the MP2 and B3LYP levels of theory. Activation energies (E _a), imaginary frequencies (υ), and Gibbs free energies (ΔG ^#) of the amine-imine and keto-enol tautomerisms and O–H internal rotations were calculated. The activation energies of amine-imine tautomerisms were in the range of 110–200 kJ/mol and for keto-enol tautomerisms were larger than 200 kJ/mol. The calculated activation energies of internal O–H rotations were smaller than 60 kJ/mol. Effect of micro-hydration on the transition state structures and activation energies of the tautomerisms were also investigated. Water molecule catalyzed the tautomerisms and decreased the activation energies of both the amine-imine and keto-enol tautomerisms about 100–120 kJ/mol.     

A Hirshfeld interpretation of the charge,spin distribution and polarity of the dipole moment of the open shell \left( {^{3} \Sigma^{ - } } \right) phosphorus halides: PF and PCl

Optimized geometries and energies, vertical excitation energies and vibrational frequencies are reported for nine cations MX₃ ⁺, with M = B, Al, Ga, and X = F, Cl, Br. Density functional theory using long-range corrected functionals, coupled cluster and multireference configuration interaction methods were applied with triple-zeta polarized basis sets. All cations were shown to be distorted from the high D_3h to the lower C_2v symmetry due to a strong pseudo Jahn–Teller effect. Geometry optimizations lead to two ²B₂ states, one with an X(axial)–M–X angle above 120°, to give a structure with one short and two long bonds (1S2L), the other having such angle below 120°, resulting in a structure with two short and one long bond (2S1L). In most cases, the 1S2L structure was found to be more stable than 2S1L, but the stabilization energies of 1S2L and 2S1L differ by no more than 0.2 eV. There is a saddle point at D_3h symmetry. Adiabatic and vertical ionization energies of MX₃ are also reported. Good to excellent agreement with available experimental data was found.     

Influence of madelung (interatomic Coulomb) energy on Wolfsberg–Helmholz calculations

A model is presented for the estimation of ionicities in molecules and complex ions. The model uses the minimization of total energy by the method of differential ionization energies. The effect of Madelung corrections to the energies is considered, and the model is refined by evaluating the covalent-bond energies. Wolfsberg–Helmholz calculations have been applied to the same type of model, also incorporating Madelung corrections. The Madelung corrections make the metal ionization energy curves less steep, and the ligand ionization energies are nearly invariant with charge. This creates a situation which has previously been artificially imposed by selecting the ligand ionization energies to give desirable terms in the Wolfsberg–Helmholz secular determinant. The effect of Madelung energy is shown to be the primary influence in describing the ionicity and total energy of a chromophore; covalent bonding effects are shown to be secondary when the ligands and the central atom have fairly different electronegativities.     

Doubly charged ion mass spectra of alkyl-substituted furans and pyrroles

Doubly charged ion mass spectra of alkyl-substituted furans and pyrroles were obtained using a double-focusing magnetic mass spectrometer operated at 3.2 kV accelerating voltage. Molecular ions were the dominant species found in doubly charged spectra of lower molecular weight heterocydic compounds, whereas the spectra of the higher weight homologues were typified by abundant fragment ions from extensive decomposition. Measured doubly charged ionization and appearance energies ranged from 22.8 to 47.9 eV. Ionization energies were correlated with values calculated using self-consistent field–molecular orbital techniques. A multichannel diabatic curve-crossing model was developed to investigate the fundamental organic ion reactions responsible for development of doubly charged ion mass spectra. Probabilities for Landau–Zener type transitions between reactant and product curves were determined and used in the collision model to predict charge-transfer cross-sections, which compared favorably with experimental cross-sections obtained using time-of-flight techniques.