Correlation energy extrapolation by intrinsic scaling. II. The water and the nitrogen molecule

The extrapolation method for determining benchmark quality full configuration-interaction energies described in preceding paper [L. Bytautas and K. Ruedenberg, J. Chem. Phys. 121, 10905 (2004)] is applied to the molecules H(2)O and N(2). As in the neon atom case, discussed in preceding paper [L. Bytautas and K. Ruedenberg, J. Chem. Phys. 121, 10905 (2004)] remarkably accurate scaling relations are found to exist between the correlation energy contributions from various excitation levels of the configuration-interaction approach, considered as functions of the size of the correlating orbital space. The method for extrapolating a sequence of smaller configuration-interaction calculations to the full configuration-interaction energy and for constructing compact accurate configuration-interaction wave functions is also found to be effective for these molecules. The results are compared with accurate ab initio methods, such as many-body perturbation theory, coupled-cluster theory, as well as with variational calculations wherever possible.     

Correlation energy extrapolation by intrinsic scaling. III. Compact wave functions

The information gained in the context of extrapolating the correlation energy by intrinsic scaling is used to shorten the full configurational expansions of electronic wave function without compromising their chemical accuracy. The truncations are accomplished by judiciously limiting the participation of the ranges of predetermined approximate sets of natural orbitals in the various excitation categories.     

Correlation energy extrapolation by intrinsic scaling. I. Method and application to the neon atom

Remarkably accurate scaling relations are shown to exist between the correlation energy contributions from various excitation levels of the configuration interaction approach, considered as functions of the size of the correlating orbital space. These relationships are used to develop a method for extrapolating a sequence of smaller configuration interaction calculations to the full configuration-interaction energy. Calculations of the neon atom ground state with the Dunning's quadruple zeta basis set demonstrate the ability of the method to obtain benchmark quality results.     

Correlation energy extrapolation by intrinsic scaling. IV. Accurate binding energies of the homonuclear diatomic molecules carbon, nitrogen, oxygen, and fluorine

The method of extrapolation by intrinsic scaling, recently introduced to obtain correlation energies, is generalized to multiconfigurational reference functions and used to calculate the binding energies of the diatomic molecules C2, N2, O2, and F2. First, accurate approximations to the full configuration interaction energies of the individual molecules and their constituent atoms are determined, employing Dunning's correlation consistent double-, triple- and quadruple zeta basis sets. Then, these energies are extrapolated to their full basis set limits. Chemical accuracy is attained for the binding energies of all molecules.     

Accurate ab initio potential energy curve of F2. I. Nonrelativistic full valence configuration interaction energies using the correlation energy extrapolation by intrinsic scaling method

The recently introduced method of correlation energy extrapolation by intrinsic scaling (CEEIS) is used to calculate the nonrelativistic electron correlations in the valence shell of the F(2) molecule at 13 internuclear distances along the ground state potential energy curve from 1.14 A to 8 A, the equilibrium distance being 1.412 A. Using Dunning's correlation-consistent double-, triple-, and quadruple-zeta basis sets, the full configuration interaction energies are determined, with an accuracy of about 0.3 mhartree, by successively generating up to octuple excitations with respect to multiconfigurational reference functions that strongly change along the reaction path. The energies of the reference functions and those of the correlation energies with respect to these reference functions are then extrapolated to their complete basis set limits. The applicability of the CEEIS method to strongly multiconfigurational reference functions is documented in detail.     

Excess free energy,enthalpy and entropy of surfactant-surfactant mixed micelle formation

Enthalpies of dilution and osmotic coefficients of sodium decylsulfate (NaDeS)-dodecyldimethylamine oxide (DDAO) mixtures in water were determined at 298 and 310 K, respectively. From the enthalpies of dilution, the apparent and then the partial molar relative enthalpies of the surfactant mixtures were calculated. From the osmotic coefficients, calculated at 298 K, the non-ideal free energies were derived. The latter were combined with the partial molar relative enthalpies to obtain the non-ideal entropies. From the apparent molar properties, using a previously reported approach, the excess thermodynamic properties for the surfactant-surfactant mixed micelle formation in water were evaluated as functions of the mixture composition at some total micellized concentration. In the whole range of the mixture composition, the excess free energy is negative, indicating that the mixed micelle formation is favoured with respect to that of pure micelles. This process is governed by the enthalpy and/or the entropy, depending on the mixture composition. The effect of the alkyl chain length was also studied by comparing the present results to those of the sodium dodecylsulfate-DDAO mixture.     

MOF-5: enthalpy of formation and energy landscape of porous materials

The first experimental thermodynamic analysis of a metal-organic framework (MOF) has been performed. Measurement of the enthalpy of formation of MOF-5 from the dense components zinc oxide (ZnO), 1,4-benzenedicarboxylic acid (H(2)BDC), and occluded N,N-diethylformamide (DEF) (if any) gave values of 78.64 ± 2.95 and 99.47 ± 3.62 kJ·[mol of Zn(4)O(BDC)(3)·xDEF](-1) for the as-made form and the desolvated structure, respectively. These as-made and desolvated enthalpies correspond to the values 19.66 ± 0.74 and 24.87 ± 0.94 kJ·(mol of Zn)(-1), respectively. The energetics of desolvated MOF-5 per mole of Zn falls in line with trends relating the enthalpy of inorganic porous materials (zeolites, zeotypes, and mesoporous materials) to molar volume. MOF-5 extends a plateauing trend first suggested by thermodynamic studies of mesoporous materials. This leveling off of the destabilization energetics as the void space swells suggests that additional void volume beyond a certain point may begin to act as a parameter "external" to the structure and not destabilize it further. This could help explain the rich landscape of large-volume MOFs and their ease of desolvation.     

Approximation of enthalpy of formation by Fourier series

A possible approximation of the enthalpy of formation of C,H,N,O-containing compounds by trigonometric Fourier series has been shown.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1389–1390, August, 1994.     

Gas-phase acidity, bond dissociation energy and enthalpy of formation of fluorine-substituted benzenes: A theoretical study

A variety of theoretical methods have been used to study the gas-phase acidity of benzene and its eleven fluorine-substituted derivatives: fluorobenzene, three isomers of difluorobenezene, three isomers of trifluorobenzene, three isomers of tetrafluorobenzene and 1,2,3,4,5-pentafluorobenzene. The high-level ab initio methods, G3//B3-LYP and CBS-QB3, are shown to reproduce experimental data to within an average of 1.9 and 1.4 kcal mol⁻¹, respectively. Of the lower-cost methods studied, M05-2X and MP2 showed the best overall performance with mean absolute deviations of just 1.2 and 1.1 kcal mol⁻¹, respectively. The effect of substitution and position on the acidity of the protons in the various compounds are studied and the structure-reactivity trends in these heterolytic C-H bond dissociation energies (BDEs) are compared with the corresponding homolytic C-H BDEs for the same species.     

Preparation,Characterization and Standard enthalpy of formation of Sr2CeO4.

Sr₂CeO₄ has been prepared by sol-combustion and co-precipitate routes and the resulting products have been characterized by XRD analysis. The molar enthalpies of solution of Sr₂CeO₄(s), Sr(NO₃)₂(s) and Ce(NO₃)₃·6H₂O(s) in 0.150 dm^–3 of (4.41 mol dm–3 H₂O₂+4.23 mol dm^–3 of HNO₃) solvent as well as the molar enthalpies of solution of Sr₂CeO₄(s), SrCl₂(s) and CeCl₃(s) in 0.150 dm³ of (1.47 mol dm^–3 H₂O₂+3.05 mol dm^–3 of HClO₄) solvent have been measured using an isoperibol type calorimeter. From these results and other auxiliary data, the standard molar enthalpy of formation of Sr₂CeO₄ has been derived to be –2277.3±3.1 kJ mol^–1 at 298.15 K. This is the first reported thermodynamic data on this compound.     

Standard enthalpy of formation of nickel trifluoride by isothermal calorimetry

The change in enthalpy in reactions of NiF₃(s) with water and aqueous solution of potassium hydroxide are measured in the isothermal calorimetry mode at 298.15 K. The standard enthalpy of formation Δ_f H° of nickel trifluoride was found to be −816 ± 6 kJ/mol.     

Cyclophanes: Simulation of the formation enthalpy by quantum-chemical methods

Comparison of experimental values of gas-phase formation enthalpy of cyclophanes with the results of semiempirical quantum-chemical simulation has revealed good linear correlation with the PM-3 data. Using the derived equation, formation enthalpies of 30 cyclophanes have been predicted.     

Correlation and prediction of ternary excess enthalpy data

Methods for predicting ternary excess enthalpies from excess enthalpy data for the three binary mixtures involved are examined and tested for forty-two sets of ternary data. In order to study the relation between the performance of the methods and the characteristics of the components in the mixture, the sets of data were classified into four groups according to the chemical nature of their components. The asymmetric equations proposed by Scatchard, Toop, and Hillert are shown to provide accurate predictions. The ratio of the standard deviations between experimental and predicted excess enthalpies and the maximum absolute value of this magnitude is 0.05 or less for most of the systems. These equations are asymmetric with respect to the numbering of components. A rule is given for selecting which component is to be designated as component 1 for systems showing endothermic mixing, exothermic mixing, or a combination of endothermic and exothermic mixing. Correlation methods are also examined and a partial differential approximant is proposed to represent the ternary contribution to the excess enthalpy.     

Electronic structure and prediction of atomization energy of naked homoleptic uranium hexacarbonyl U(CO)6

Our ab initio all-electron fully relativistic Dirac-Fock and nonrelativistic Hartree-Fock self-consistent field (SCF) calculations predict the octahedral (Oh) uranium hexacarbonyl U(CO)6 to be bound with the calculated atomization energy of 49.84 and 48.76 eV at the predicted U-C bond lengths (assuming the C-O bond distance fixed at 1.17 A) of 2.53 and 2.63 A, respectively. Moreover, our all-electron fully relativistic Dirac-Fock SCF calculations predict U(CO)6 to be lower in energy by 3.90 eV with respect to dissociation into U plus six CO ligands. We predict U(CO)6 (Oh) to be very stable in view of our predicted large atomization energy (approximately 49 eV) and stability (approximately 4 eV) with respect to dissociation into U plus six CO molecules. Innovative techniques should be devised for the synthesis of uranium hexacarbonyl since the usual synthetic methods have failed so far for this naked actinide hexacarbonyl.     

Cationic lanthanide complexes of neutral tripodal N,O ligands: enthalpy versus entropy-driven podate formation in water

The cationic lanthanide complexes of two neutral tripodal N,O ligands, tpa (tris[(2-pyridyl)methyl]amine) and tpaam (tris[6-((2-N,N-diethylcarbamoyl)pyridyl)methyl]amine) are studied in water. The analysis of the proton lanthanide induced NMR shifts indicate that there is no abrupt structural change in the middle of the rare-earth series. Unexpectedly, the formation constant values of the lanthanide podates of tpaam and tpa in D2O at 298 K are similar, suggesting that the addition of the three amide groups to the ligand tpa does not lead to any increase in stability of the lanthanide complexes of tpaam in respect to tpa, even though the amide groups are coordinated to the metal in aqueous solution. The measurement of the enthalpy and entropy changes of the complexation reactions shows that the two similar ligands tpa and tpaam have different driving forces for lanthanide complexation. Indeed, the formation of tpa podates benefits from an exothermic enthalpy change associated with a small entropy change, whereas the complexation reaction with tpaam is clearly entropy-driven though opposed by a positive enthalpy change. The hydration states of the europium complexes were measured by luminescence and show the coordination of 4-5 water ligands in [Eu(tpa)]3+ whereas there are only 2 in [Eu(tpaam)]3+. Therefore the heptadentate ligand tpaam releases the translational entropy of more water molecules than does the tetradentate ligand tpa.     

L-苏糖酸铜的制备及其标准生成焓

L 苏糖酸作为金属离子的载体,可使金属离子易与氨基酸或蛋白质结合而被动物吸收和利用[1]。本文以L 苏糖酸与Cu2(OH)2CO3·xH2O反应后的溶液浓缩加无水甲醇制得水合物Cu(C4H6O5)·0 5H2O(经HPLC分析,纯度>99 9%),用化学分析、元素分析、IR光谱、TD DTG和量热法进行了表征。1　实验部分1 1　试剂与仪器L 抗坏血酸(Vc)、B.R.(东北制药总厂);H2O2、CaCO3、H2C2O4和Cu2(OH)2CO3·xH2O均为A.R.(西安化学试剂厂);2400型元素分析仪(PE公司);Cu2+含量用Na2S2O3滴定法测定;TG 7型热重分析仪(PE公司);BRUKEREQUINOX 5…     

Electronic processes induced by high energy H+, H 2 + and H 3 + -ions: A scaling relation

A scaling relation is proposed which interrelates measurable quantities in the field of atomic collision physics performed with high velocity H⁺, H ₂ ⁺ and H ₃ ⁺ -ions. The relation may be written as $$Q(H^ + ) - 2*Q(H_2^ + ) + Q(H_3^ + ) = 0,$$ whereQ denotes an excitation or ionization cross section or a total or differential secondary particle yield evaluated at the same projectile velocity. The scaling relation will be tested by comparison with experimental data of yields and spectra from ion-induced secondary electron emission measurements and with cross section data for excitation and ionization of atoms and molecules. In general very good agreement is observed for high projectile velocities (v>2 a.u.).     

The ultraviolet photochemistry of phenylacetylene and the enthalpy of formation of 1,3,5-hexatriyne.

The ultraviolet photochemistry of phenylacetylene was studied in a molecular beam at 193 nm. The only primary photofragments observed were HCCH (acetylene) and C(6)H(4). Some of the C(6)H(4) molecules were found to decompose to 1,3,5-hexatriyne and molecular hydrogen. An enthalpy of formation of DeltaH(f) < or = 160 +/- 4 kcal mol(-1) was determined for 1,3,5-hexatriyne from the energetic threshold for this process. This experimentally determined value agrees well with our ab initio calculations performed at the G2 level of theory. Angular distribution measurements for the HCCH + C(6)H(4) channel yielded an isotropic distribution and were attributed to a long-lived intermediate and ground-state dissociation. An exhaustive search yielded no evidence for the phenyl + ethynyl or the atomic hydrogen elimination channels even though these were observed in the pyrolytic studies of phenylacetylene [Hofmann, J.; Zimmermann, G.; Guthier, K.; Hebgen, P.; Homann, K. H. Liebigs Ann. 1995, 631, 1995. Guthier, K.; Hebgen, P.; Hofmann, K. H.; Zimmermann, G. Liebigs Ann. 1995, 637, 1995].