QTAIM charge-charge flux-dipole flux interpretation of electronegativity and potential models of the fluorochloromethane mean dipole moment derivatives.

Infrared fundamental vibrational intensities and quantum theory atoms in molecules (QTAIM) charge-charge flux-dipole flux (CCFDF) contributions to the polar tensors of the fluorochloromethanes have been calculated at the QCISD/cc-pVTZ level. A root-mean-square error of 20.0 km mol(-1) has been found compared to an experimental error estimate of 14.4 and 21.1 km mol(-1) for MP2/6-311++G(3d,3p) results. The errors in the QCISD polar tensor elements and mean dipole moment derivatives are 0.059 e when compared with the experimental values. Both theoretical levels provide results showing that the dynamical charge and dipole fluxes provide significant contributions to the mean dipole moment derivatives and tend to be of opposite signs canceling one another. Although the experimental mean dipole moment derivative values suggest that all the fluorochloromethane molecules have electronic structures consistent with a simple electronegativity model with transferable atomic charges for their terminal atoms, the QTAIM/CCFDF models confirm this only for the fluoromethanes. Whereas the fluorine atom does not suffer a saturation effect in its capacity to drain electronic charge from carbon atoms that are attached to other fluorine and chlorine atoms, the zero flux electronic charge of the chlorine atom depends on the number and kind of the other substituent atoms. Both the QTAIM carbon charges (r = 0.990) and mean dipole moment derivatives (r = 0.996) are found to obey Siegbahn's potential model for carbon 1s electron ionization energies at the QCISD/cc-pVTZ level. The latter is a consequence of the carbon mean derivatives obeying the electronegativity model and not necessarily to their similarities with atomic charges. Atomic dipole contributions to the neighboring atom electrostatic potentials of the fluorochloromethanes are found to be of comparable size to the atomic charge contributions and increase the accuracy of Siegbahn's model for the QTAIM charge model results. Substitution effects of the hydrogen, fluorine, and chlorine atoms on the charge and dipole flux QTAIM contributions are found to be additive for the mean dipole derivatives of the fluorochloromethanes.

The infrared vibrational intensities and polar tensors of HFCO and DFCO.

The infrared vibrational intensities of HFCO and DFCO have been calculated at the B3LYP/cc-pVTZ, MP2(FC)/6-311++G(3d,3p) and QCISD(FU)/aug-cc-pVTZ levels. All calculations predict the isotopomers to have identical intensity sums, within about 1 km mol(-1). This is in contrast with experimental intensity sum results reported in the literature. Dipole moment derivative directions calculated by the three methods are in excellent agreement for all in-plane normal coordinates. All the theoretical polar tensor elements are also in good agreement with each other having standard deviations varying between 0.003 and 0.043 e. The oxygen and fluorine atoms have negative mean derivatives (approximately -0.6 e), whereas the carbon mean derivative is very positive (approximately +1.1e) and the hydrogen one is almost zero (approximately +0.03 e). The HFCO theoretical intensity sums calculated by all three methods as well as their carbon and oxygen mean dipole moment derivatives are in good agreement with those estimated from the experimental intensities and atomic mean derivatives of H2CO and F2CO.

The infrared fundamental intensities and polar tensor of CH3NC.

The molecular force field and polar tensor of methyl isocyanide have been determined from its gas phase vibrational frequencies and infrared intensities. Quantum chemical results from MP2(FC), B3LYP and quadratic configuration interaction calculation including single and double substitutions procedures using a 6-311 + +G(3d,3p) basis set have been used to determine the signs of the dipole moment derivatives with respect to the normal coordinates as well as estimate individual fundamental intensities of the overlapped v1-v5 and v3-v6 band systems. Principal component graphical representations of the A1 and E symmetry polar tensor elements were useful in determining preferred sets of tensor elements. The mean dipole moment derivative (GAPT charge) of the methyl carbon in CH3NC, 0.347 e, is between the corresponding values in CH3CN, 0.110 e, and CH3F, 0.541 e. The mean dipole moment derivatives obtained here indicate the correct 1s methyl carbon ionization energy as 293.35 eV which is 0.98 eV higher than the corresponding ionization energy of the terminal atom.

Electrochemical oxidation of imazapyr with BDD electrode in titanium substrate.

In this work we have studied the treatment of imazapyr by electrochemical oxidation with boron-doped diamond anode. Electrochemical degradation experiments were performed in a one-compartment cell containing 0.45 L of commercial formulations of herbicide in the pH range 3.0-10.0 by applying a density current between 10 and 150 mA cm(-2) and in the temperature range 25-45 °C. The maximum current efficiencies were obtained at lower current densities since the electrochemical system is under mass transfer control. The mineralization rate increased in acid medium and at higher temperatures. The treatment was able to completely degrade imazapyr in the range 4.6-100.0 mg L(-1), although the current charge required rises along with the increasing initial concentration of the herbicide. Toxicity analysis with the bioluminescent bacterium Vibrio fischeri showed that at higher pollutant concentrations the toxicity was reduced after the electrochemical treatment. To clarify the reaction pathway for imazapyr mineralization by OH radicals, LC-MS/MS analyses we performed together with a theoretical study. Ions analysis showed the formation of high levels of ammonium in the cathode. The main final products of the electrochemical oxidation of imazapyr with diamond thin film electrodes are formic, acetic and butyric acids.

A theoretical systematic study of a series of isocyanopolyynes.

Several isocyanopolyynes, HCnNC (n=0, 2,…,16), are analyzed in this theoretical work. We performed calculations at MP2/cc-pVTZ (n=0-16), CCSD/cc-pVDZ (n=0-12) and CCSD/cc-pVTZ (n=0-6) levels. The dipole moments from the best treatment, CCSD/cc-pVTZ, are in much closer agreement with those obtained in CCSD/cc-pVDZ calculations (deviations up to 0.05 Debye) than with the results from MP2/cc-pVTZ (discrepancies that can reach 0.55 Debye). Moreover, the CCSD/cc-pVTZ level yields values in excellent accordance with experimental dipole moments for HNC and HC2NC. Hence, this allows concluding that the correct treatment of electron correlation is more important than increments in basis sets for this electric property in isocyanopolyynes and CCSD/cc-pVDZ values are indicated as the best estimates available for large isocyanopolyynes. The findings from infrared intensities of fundamental vibrational bands are also similar (mean deviations of 3.1 km mol(-1) for CCSD/cc-pVDZ and 12.6 km mol(-1) for MP2/cc-pVTZ with respect to CCSD/cc-pVTZ results). Thus, we decided to use the charge - charge flux - dipole flux (CCFDF) model from multipoles given by the Quantum Theory of Atoms in Molecules (QTAIM), which were obtained at the CCSD/cc-pVDZ level, to investigate the variations in infrared intensities of some selected modes along these systems. The intensity of the band associated with CH stretching shows an increase with the size of these molecules (from 96 to 146 km mol(-1) between n=4 and 12) that is readily explained by variations in the charge flux contribution to this mode, in a similar way as found before for cyanopolyynes. Furthermore, the degenerate CH bending vibrations present almost constant intensities in these isocyanopolyynes (around 37-38 km mol(-1) from n=4 up to n=12) and this pattern is supported by CCFDF/QTAIM contributions. The band mostly assigned to stretching of the NC triple bond, which can also be described as asymmetric stretching mode of all pairs of adjacent triple bonds, shows an increase of intensity up to n=6 and is associated to values around 96-102 km mol(-1) in the remaining larger members. Another important mode detected is a symmetric stretching of NC and CC triple bonds belonging to the isonitrile end (between 66 and 101 km mol(-1) when n=6-12) for which the charge contribution is nearly constant and dynamic contributions change in a more complicated way. The most intense fundamental band in each isocyanopolyyne from n=4 to 12 is assigned to vibrations of triple bonds in both ends of these systems (from 129 to 164 km mol(-1)) and an alternating behavior according with even or odd numbers of CC triple bonds is observed for these values and also for respective CCFDF/QTAIM contributions. Finally, this work also brings values derived from regressions that are indicated as the best estimates of rotational constants and dipole moments to be used for detection of large isocyanopolyynes in the interstellar medium.