Spectroscopic calculation of CH bond dissociation energy in the series of chloro derivatives of methane, ethane, and propane

The bond-dissociation energy of CH bonds in chloro derivatives of methane, ethane, and propane has been determined by spectroscopic and quantum chemical methods. Spectroscopic values for CH bond dissociation energy were computed, basing on fundamental absorption bands in the anharmonic approximation, by the variational method with the use of the Morse anharmonic basis. Quantum chemical computations were performed using the basis 6-311G(3df, 3pd)/B3LYP. There are discussed the obtained regularities of changes in the bond dissociation energy when the structure of a molecule is changed.     

Spectroscopic calculation of CH bond dissociation energy for aliphatic derivatives from the ethylene series

The bond-dissociation energy of CH bonds in molecules of the ethylene homological series has been determined by spectroscopic and quantum chemical methods. Spectroscopic values for the CH bond dissociation energy were calculated based on the fundamental absorption bands in the anharmonic approximation by the variation method using the Morse anharmonic basis. Quantum chemical computations were performed with 6-311G(3d, 3p)/B3LYP basis. There are discussed the obtained regularities of changes in the bond dissociation energy when the structure of a molecule is changed.     

Spectroscopic calculation of CH bond dissociation energies for the bromo derivatives of alkanes,alkenes, and arenes

The CH bond dissociation energies were determined for the bromo derivatives of methane, ethane, propane, cyclopropane, ethane, propene, and benzene by the spectroscopic and quantum-chemical methods. The spectroscopic values of the CH bond dissociation energies were obtained from the fundamental absorption bands by the variational method in an anharmonic approximation using the Morse-harmonic basis. Quantum-chemical calculations were performed using the 6-311G(3df, 3pd)/B3LYP basis. The resulting tendencies of variation of the bond dissociation energies due to changes in the molecular structure are discussed.     

Dissociation Constants of Silanol Groups of Silic Acids: Quantum Chemical Estimations

Dissociation constants of silanol groups on the silica surface are calculated with the DFT quantum chemical method using B3LYP and M06 functionals. Structural features of silanol fragments and the presence of hydrogen-bonded water clusters are shown to have significant effects on pK_a values of silanol groups. In particular, pK_a values are shown to vary widely depending on the features of the system of hydrogen bonds.     

Theoretical Study of Substituent Effect in Aryl Group Migration in (<Emphasis Type="Italic">para</Emphasis>-C<Subscript>6</Subscript>H<Subscript>4</Subscript>X)Mn(CO)5 Complexes

In this study, we report substituent effect on aryl group migration in (para-C₆H₄X)Mn(CO)₅ complexes using mpw1pw91 quantum chemical calculations. These calculations reveal good linear relationships between barrier energy (ΔE), activation energy (ΔH^?), activation free energy (ΔG^?) values and rate constants with Hammett constants of X-substituents. The occupancy values of Mn–CO_cis and Mn–C(O)-(para-C₆H₄X) bonds in reactant, transition state and product were calculated by Natural bond orbital (NBO) method.     

Internal rotation and equilibrium structure of the 2-methyl-2-nitropropane molecule from joint processing of gas phase electron diffraction data,vibrational and microwave spectroscopy data,and quantum chemical calculation results

The structure and internal rotation of the 2-methyl-2-nitropropane molecule is studied by electron diffraction and quantum chemical calculations with the use of microwave and vibrational spectroscopy data. The electron diffraction data are analyzed within the general intramolecular anharmonic force field model and the quantum chemical pseudoconformer model, considering the adiabatic separation of the degree of freedom of large amplitude motion, i.e., the internal rotation of the NO₂ group. The equilibrium eclipsed configuration of the C _s symmetry molecule has the following experimental bond lengths and valence angles: r _e(N=O) = 1.226//1.226(8) Å, r _e(C–N)//r _e(C–C) = 1.520//1.515/1,521(4) Å, ∠_еC–C–N = = 109.1/106,1(8)°, ∠_еO=N=O = 124.2(6)°, ∠_eC–C–H_avg = 110(3)°. The equilibrium geometry parameters are well consistent with MP2/cc-pVTZ quantum chemical calculations and microwave spectroscopy data. The thermally average parameters previously obtained within the small vibration model show a satisfactory agreement with the new results. The electron diffraction data used in this work do not allow a reliable determination of the barrier to internal rotation. However, at a barrier of 203(2) cal/mol, which is derived from the microwave study, it follows from the electron diffraction data that the equilibrium configuration must correspond to an eclipsed arrangement of C–C and N=O bonds, which is also consistent with the results of quantum chemical calculations of various levels.     

Monoethanolamine: Cluster Structure Motives

Structures and energy characteristics of clusters composed of monoethanolamine molecules are analyzed using the results of quantum chemical calculations carried out at the density functional level (DFT-B3LYP/6-31G(d,p)) and in the second order of the Møller—Plesset perturbation theory (MP2/6-31G(d, p)). Similar structural motives of hydrogen-bond networks are found in clusters that correspond to the gas-phase aggregation of initially independent molecules and the detachment of thermally distorted crystal lattice fragments. The energies of different hydrogen bonds are compared, and structural motives atypical of crystalline monoethanolamine are found. The studied clusters are shown to be prototypes of the inherent structural fragments of liquid monoethanolamine.     

A quantum-chemical study of the structure and conformational dynamics of the acrolein molecule in the ground electronic state

The geometric parameters (including vibrationally averaged parameters), energy differences (ΔE) between the s-cis and s-trans conformers, and barrier to internal rotation (V _t ) were calculated for the acrolein molecule CH₂=CHCHO by various quantum-chemical methods (MP2, DFT, CASSCF, QCISD, CCSD(T), and MR-AQCC). The MP2 and B3LYP methods were used to calculate internal rotation potential functions and vibrational frequencies; the calculations were performed in various anharmonic approximations. To refine the ΔE and V _t values, two-dimensional (using a basis set of atomic orbitals) VFPA extrapolation procedure was applied, which allowed the results to be estimated in the FCI/CBS approximation taking into account nonadiabaticity, core correlation effects, and changes in the difference between zero point energies.     

Quantum chemical simulation of hydration and association of phenylalanine in solution

A quantum chemical simulation of the structure of a hydrated phenylalanine zwitterion, dimers and larger phenylalanine associates in an aqueous solution is performed by the hybrid B3LYP density functional method with the 6-31G++(d,p) basis set. It is shown that the association of the amino acid occurs by the formation of hydrogen bonds between phenylalanine amino carboxyl groups involving water molecules.     

Internal Rotation and Equilibrium Structure of the Bromonitromethane Molecule According to Gas Electron Diffraction Data and Quantum Chemical Calculations

The structure and internal rotation of the bromonitromethane molecule are studied using electron diffraction analysis and quantum chemical calculations. The electron diffraction data are analyzed within the models of a general intramolecular anharmonic force field and quantum chemical pseudoconformers to account for the adiabatic separation of a large amplitude motion associated with the internal rotation of the NO₂ group. The following experimental bond lengths and valence angles are obtained for the equilibrium orthogonal configuration of the molecule with C_s symmetry: r_e(N=O) = 1.217(5) Å, r_e(C–N) = 1.48(2) Å, r_e(C–Br) = 1.919(5) Å, ∠_еBr–C–N = 109.6(9)°, ∠_еO=N=O = 125.9(9)°. The equilibrium geometry parameters are in good agreement with CCSD(T)/cc-pVTZ calculations. Thermally averaged parameters are calculated using the equilibrium geometry and quadratic and cubic quantum chemical force constants. The barrier to internal rotation cannot be determined reliably based on the electron diffraction data used in this work. There is a 82% probability that the equilibrium configuration with orthogonal C–Br and N=O bonds is most preferable, and internal rotation barrier does not exceed 280 cm^-1, which agrees with CCSD(T)/cc-pVTZ calculations.     

Hydrogen-Bonding Interaction in a Complex of Amino Acid with <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-Dimethylformamide Studied by DFT Calculations

Theoretical studies on hydrogen-bonded complexes between amino acids (glycine, alanine and leucine) and N,N-dimethylformamide (DMF) in gas phase have been carried out using density functional theory (DFT) and ab initio calculations at the B3LYP/6-311++G** and MP2/6-311++G** theory levels. The structures, binding energy, stretching frequency and bond characteristics of the mentioned complexes were calculated. The NH₂ and COOH groups of amino acids form different types of hydrogen bonds with the DMF molecule, as well as alkyl side chains. High binding energy suggests multiple hydrogen bonds present in one complex. The nearly linear OH???O and NH???O contacts are stronger than a conventional hydrogen bond interaction with their H???O separation between 1.74 and 2.14 Å. The weaker CH???O H-bond is also discussed as being a crucial interaction in biological systems involving amino acids. The formation of this interaction results in a blue shift in the CH stretching frequency.     

Zur Strukturaufklärung der Isomeren von α-Oximinocarbonsäureestern

The theoretical and experimental dipole moments for a number ofsyn- andanti-α-oximino esters are determined.NMR- andIR-spectra are reported. On the basis of these and previous chemical investigations the preferred steric structures of thesyn- andanti-forms are ascertained. Two rotational isomers exist in the same degree with thesyn-forms. Due to resonance effects and hydrogen bonds they are relatively stable.     

SAMPL6: calculation of macroscopic p<Emphasis Type="Italic">K</Emphasis><Subscript>a</Subscript> values from ab initio quantum mechanical free energies

Macroscopic pK_a values were calculated for all compounds in the SAMPL6 blind prediction challenge, based on quantum chemical calculations with a continuum solvation model and a linear correction derived from a small training set. Microscopic pK_a values were derived from the gas-phase free energy difference between protonated and deprotonated forms together with the Conductor-like Polarizable Continuum Solvation Model and the experimental solvation free energy of the proton. pH-dependent microstate free energies were obtained from the microscopic pK_as with a maximum likelihood estimator and appropriately summed to yield macroscopic pK_a values or microstate populations as function of pH. We assessed the accuracy of three approaches to calculate the microscopic pK_as: direct use of the quantum mechanical free energy differences and correction of the direct values for short-comings in the QM solvation model with two different linear models that we independently derived from a small training set of 38 compounds with known pK_a. The predictions that were corrected with the linear models had much better accuracy [root-mean-square error (RMSE) 2.04 and 1.95 pK_a units] than the direct calculation (RMSE 3.74). Statistical measures indicate that some systematic errors remain, likely due to differences in the SAMPL6 data set and the small training set with respect to their interactions with water. Overall, the current approach provides a viable physics-based route to estimate macroscopic pK_a values for novel compounds with reasonable accuracy.     

Concerted cycloaddition reactions: a study using the parabolic model and quantum chemical modeling

Concerted cycloaddition reactions were studied by the method of intersecting parabolas (M3IP) and quantum chemical calculations. Experimental data were processed within the framework of the M3IP method and an algorithm for calculating the activation energies (E) and rate constants (k) for reactions from the enthalpies of reactions was developed. The parameters E and k for twelve cycloaddition reactions not studied previously were calculated. Factors affecting the activation energies were established and evaluated; these include the enthalpy of reaction, substituents, and the molecular structure of reactants. Quantum chemical modeling and topological analysis of transition states (TS) of six concerted cycloaddition reactions were performed. Depending on structure of the starting olefins, the TS of reactions can have either a symmetric or asymmetric geometry. This influences their electronic structures, the energies of chemical bonds, and the activation energies of reactions. A comparison of the activation energy values obtained from the M3IP and DFT(B3lyp/6-311++G** ) calculations revealed good agreement between them.     

On the accuracy of <Emphasis Type="Italic">ab initio</Emphasis> calculations of absolute band intensities in the IR spectra of molecules

Absolute intensities are calculated in the harmonic approximation for the IR spectrum of 18 hydrocarbons, oxygen- and nitrogen-containing organic compounds. The quantum chemical calculation is carried out in the 6-311G(3df,3pd) basis set. The calculated data are compared to the experimental values of absolute absorption intensities. It is found that calculations in the HF approximation substantially overestimate (on average by 87%) the integral absolute intensity of fundamental vibrations in the 575–4000 cm^?1 range. Most part of this overestimation falls on the stretching vibrations with large amplitudes (C-H and C=O bonds). When the MP2 method is used without electron correlation treatment, this overestimation decreases to 22% and becomes more uniform in the whole spectral region.     

Relation between chemical composition of sols and surface free energy of inorganic-organic films

The presented study deals with relation between chemical composition of precursor sols and surface free energy of inorganic-organic films. Inorganic-organic films were prepared from precursor sols in “tetraethoxysilane (TEOS) - triethoxy(octyl)silane (OTES) - distilled water - nitric acid - isopropyl alcohol” system. The fifteen sols were prepared, where the ratio of K?=?x(OTES)/(x(TEOS)?+?x(OTES)) varied from 0 to 0.5 and ratio of R?=?x(H₂O)/(x(TEOS)?+?x(OTES)) varied from 2 to 6. The relationship between chemical composition and surface free energy of inorganic-organic films was quantified by model selection approach. Model, which describes the studied relationship in the best way, was selected on the basis of Akaike information criterion. Based on the analysis of selected (the best describing) model, it was found out that the surface free energy as well as its dispersion and polar component are dependent only on K ratio in observed range of K and R values. Form the physico-chemical aspect, the observed dependences of surface free energy, its dispersive and polar component on chemical composition of precursor sols are explained by the influence of octyl groups on the sequences of hydrolysis and condensation reactions leading to formation of particles in precursor sol. In addition, the arrangement of octyl groups is used for explanation of particles arrangement on film surface.

Open image in new window

     

Gas electron diffraction and quantum chemical studies of the molecular structure of 2-nitrobenzenesulfonic acid

A combined gas electron diffraction and quantum chemical (B3LYP/6-311+G**, B3LYP/cc-pVTZ) study of the molecular structure of 2-nitrobenzenesulfonic acid (2-NBSA) is performed. Quantum chemical calculations show that the 2-NBSA molecule has five conformers, and the Gibbs energy of one of them is lower by more than 4.5 kcal/mol than the energy of the other conformers. It is found experimentally that the saturated vapor of 2-NBSA at T = 394(5) K contains only the low-energy conformer that has an intramolecular hydrogen bond between the H atom of the hydroxyl group and one of the O atoms of the NO₂ group. The C-C-S-O(H) torsion angle determining the position of the S-O(H) bond is ?72(7)°, while the NO₂ group is substantially turned relative to the benzene ring plane (C1-C2-N-O = 40(5)°). The following experimental values of the internuclear distances are obtained for this conformer (Å): r _h1(C-H)_av = 1.07(2), r _h1(C-C)_av = 1.401(4), r _h1(C-S) = 1.767(6), r _h1(S=O)_av = 1.412(4), r _h1(S-O) = 1.560(6), r _h1(N-O)_av = 1.217(5), r _h1(C-N) = 1.461(8), r _h1(O-H) = 0.99(3).     

Ro-vibrating energy states of a diatomic molecule in an empirical potential

An approximate analytical solution of the Schrödinger equation is obtained to represent the rotational–vibrational (ro-vibrating) motion of a diatomic molecule. The ro-vibrating energy states arise from a systematical solution of the Schrödinger equation for an empirical potential (EP) V _±(r) = D _e {1 ? (?/δ)[coth (ηr)]^±1/1 ? (?/δ)}² are determined by means of a mathematical method so-called the Nikiforov–Uvarov (NU). The effect of the potential parameters on the ro-vibrating energy states is discussed in several values of the vibrational and rotational quantum numbers. Moreover, the validity of the method is tested with previous models called the semiclassical (SC) procedure and the quantum mechanical (QM) method. The obtained results are applied to the molecules H₂ and Ar₂.