Anharmonic vibrational frequency shifts upon interaction of phenol+ with the open shell ligand O2. The performance of DFT methods versus MP2

Anharmonic vibrational frequency shifts of the phenol(+) O-H stretching mode upon complex formation with the open-shell ligand O(2) were computed at several DFT and MP2 levels of theory, with various basis sets, up to 6-311++G(2df,2pd). It was found that all DFT levels of theory significantly outperform the MP2 method with this respect. The best agreement with the experimental frequency shift for the hydrogen-bonded minimum on the potential energy surfaces was obtained with the HCTH/407 functional (-93.7 cm(-1) theoretical vs -86 cm(-1) experimental), which is a significant improvement over other, more standard DFT functionals (such as, e.g., B3LYP, PBE1PBE), which predict too large downshifts (-139.9 and -147.7 cm(-1), respectively). Good agreement with the experiment was also obtained with the mPW1B95 functional proposed by Truhlar et al. (-109.2 cm(-1)). We have attributed this trend due to the corrected long-range behavior of the HCTH/407 and mPW1B95 functionals, despite the fact that they have been designed primarily for other purposes. MP2 method, even with the largest basis set used, manages to reproduce only less than 50% of the experimentally detected frequency downshift for the hydrogen-bonded dimer. This was attributed to the much more significant spin contamination of the reference HF wave function (compared to DFT Kohn-Sham wave functions), which was found to be strongly dependent on the O-H stretching vibrational coordinate. All DFT levels of theory outperform MP2 in the case of computed anharmonic OH stretching frequency shifts upon ionization of the neutral phenol molecule as well. Besides the hydrogen-bonded minimum, DFT levels of theory also predict existence of two other minima, corresponding to stacked arrangement of the phenol(+) and O(2) subunits. mPW1B95 and PBE1PBE functionals predict a very slight blue shift of the phenol(+) O-H stretching mode in the case of stacked dimer with the nearly perpendicular orientation of oxygen molecule with respect to the phenolic ring, which is entirely of electrostatic origin, in agreement with the experimental observations of an additional band in the IR photodissociation spectra of phenol(+)-O(2) dimer [Patzer, A.; Knorke, H.; Langer, J.; Dopfer, O. Chem. Phys. Lett. 2008, 457, 298]. The structural features of the minima on the studied PESs were discussed in details as well, on the basis of NBO and AIM analyses.     

Unexpected frequency shifts and linewidth changes for rovibrational lines in the infrared emission spectra of CO2 excited by active nitrogen

Fourier transform emission spectra from flowing CO₂ excited by active nitrogen have been recorded in the 4.5 μm region, with a resolution of 0.0054 cm⁻¹, for different time intervals between the mixing of the two gases and observation of the emission. Significant frequency shifts (reaching 30 times the absolute uncertainty of the experimental frequencies) and linewidth changes are observed depending on the time interval and the value of the quantum number v₃, for thousands of rovibrational lines belonging to v₁v¹₂v₃ → v₁v¹₂(v₃-1) vibrational transitions.     

The effects of solute-solvent electrostatic interactions on solvatochromic shifts in supercritical CO2

Solvent clustering around attractive solutes is an important feature of supercritical solvation. We examine here the effects of the local density enhancement on solvatochromic shifts in electronic absorption and emission spectra in supercritical CO2. We use molecular dynamics (MD) simulation to study the spectral line shifts for model diatomic solutes that become more polar upon electronic excitation. The electronic transition is modeled as either a change from a quadrupolar to a dipolar solute charge distribution or as an increase in the magnitude of the solute dipole. Our main focus is on the density dependence of the line shifts at 320 K, which corresponds to about 1.05 times the solvent critical temperature, Tc, but results for higher temperatures are also obtained in order to determine the behavior of the line shifts in the absence of local density enhancement. We find that the extent of local density enhancement at 1.05Tc is strongly correlated with solute-solvent electrostatic attraction and that the density dependence of the emission line shifts resembles the behavior of the effective local densities, rho(eff), obtained from the first-shell coordination numbers. The differences that are seen are shown to be due to solute-solvent orientational correlations which provide an additional source of enhancement for electrostatic solvation energies and spectral line shifts.     

Memory effects in the NMR frequency shifts

The narrowing of the heat-bath correlation function by decreasing the sample temperature in a molecular system with a cooperative motion, causes the shifting of the NMR resonance frequency, as predicted by the memory-function approach.     

Measurements of infrared frequency shifts in stressed polymers

A difference-spectrum method is used to measure vibrational frequency shifts in mechanically stressed polymers. It is shown that the peak-to-peak height of the difference-spectrum intensity profile is a linear function of small frequency shifts with a slope inversely proportional to the band halfwidth for Lorentzian or Gaussian bands. The method is applied to measure frequency shifts in uniaxially stressed ultraoriented isotactic polypropylene films, using a double beam infrared grating dispersion spectrometer with a nonstressed sample in the reference beam. It is shown that frequency shifts can be measured with an accuracy of better than 0.01 cm^?1 using the difference-spectrum method.     

Anharmonic interactions and Fermi resonance in crystals CS2

The Raman spectrum of crystal CS₂ in the ω₁; 2ω₂ Fermi resonance region is discussed using the Green function formalism. Single site cubic anharmonicity strongly perturbs the manifold of ω₂+w₂ excitations. Conditions for th appearance of resonances and bound states are analyzed in terms of coupling strength and relative distance of unpertubed ω₁ and 2ω₂ levels. The experimental Raman spectrum is intepreted assuming that a resonance is present near the edge of the two-phonon continuum. Using known molecular parameters and a dipole-dipole intermolecular potential a good agreement is obtained between the calculated and observed Raman spectrum both as to the band positions and intensities.     

Effects of the crystalline structure of Ga2O3 on the photocatalytic activity for CO production from CO2

Ga₂O₃ samples with different crystalline structures were prepared by calcination of a gallium nitrate powder around 800 K. Ga₂O₃ samples with mixed phases of γ and β showed high photocatalytic activity for CO production from CO₂ reduction with water, and the activity was even higher than that for an Ag-loaded β-Ga₂O_3. The photocatalytic activity increased with time. The increase was attributed to the appearance of GaOOH resulting from the interaction of Ga₂O₃ with water during the reaction as revealed by XRD and XPS analyses. In situ FT-IR measurements revealed that bicarbonates and bidentate carbonate species were adsorbed on GaOOH. Therefore, the increase of the photocatalytic activity with time would be derived from the formation of GaOOH phase on the γ-Ga₂O₃ and β-Ga₂O₃ sample.     

MP2 calculation of 77Se NMR chemical shifts taking into account relativistic corrections

The main factors affecting the accuracy and computational cost of the Second‐order Möller‐Plesset perturbation theory (MP2) calculation of ⁷⁷Se NMR chemical shifts (methods and basis sets, relativistic corrections, and solvent effects) are addressed with a special emphasis on relativistic effects. For the latter, paramagnetic contribution (390–466 ppm) dominates over diamagnetic term (192–198 ppm) resulting in a total shielding relativistic correction of about 230–260 ppm (some 15% of the total values of selenium absolute shielding constants). Diamagnetic term is practically constant, while paramagnetic contribution spans over 70–80 ppm. In the ⁷⁷Se NMR chemical shifts scale, relativistic corrections are about 20–30 ppm (some 5% of the total values of selenium chemical shifts). Solvent effects evaluated within the polarizable continuum solvation model are of the same order of magnitude as relativistic corrections (about 5%). For the practical calculations of ⁷⁷Se NMR chemical shifts of the medium‐sized organoselenium compounds, the most efficient computational protocols employing relativistic Dyall's basis sets and taking into account relativistic and solvent corrections are suggested. The best result is characterized by a mean absolute error of 17 ppm for the span of ⁷⁷Se NMR chemical shifts reaching 2500 ppm resulting in a mean absolute percentage error of 0.7%. Copyright © 2015 John Wiley & Sons, Ltd.     

Sticking of CO to crystalline and amorphous ice surfaces

We present results of classical trajectory calculations on the sticking of hyperthermal CO to the basal plane (0001) face of crystalline ice Ih and to the surface of amorphous ice Ia. The calculations were performed for normal incidence at a surface temperature Ts = 90 K for ice Ia, and at Ts = 90 and 150 K for ice Ih. For both surfaces, the sticking probability can be fitted to a simple exponentially decaying function of the incidence energy, Ei: Ps = 1.0e(-Ei(kJ/mol)/90(kJ/mol)) at Ts = 90 K. The energy transfer from the impinging molecule to the crystalline and the amorphous surface is found to be quite efficient, in agreement with the results of molecular beam experiments on the scattering of the similar molecule, N2, from crystalline and amorphous ice. However, the energy transfer is less efficient for amorphous than for crystalline ice. Our calculations predict that the sticking probability decreases with Ts for CO scattering from crystalline ice, as the energy transfer from the impinging molecule to the warmer surfaces becomes less efficient. At high Ei (up to 193 kJ/mol), no surface penetration occurs in the case of crystalline ice. However, for CO colliding with the amorphous surface, a penetrating trajectory was observed to occur into a large water pore. The molecular dynamics calculations predict that the average potential energy of CO adsorbed to ice Ih is -10.1 +/- 0.2 and -8.4 +/- 0.2 kJ/mol for CO adsorbed to ice Ia. These values are in agreement with previous experimental and theoretical data. The distribution of the potential energy of CO adsorbed to ice Ia was found to be wider (with a standard deviation sigma of 2.4 kJ/mol) than that of CO interacting with ice Ih (sigma = 2.0 kJ/mol). In collisions with ice Ia, the CO molecules scatter at larger angles and over a wider distribution of angles than in collisions with ice Ih.     

Quantum chemical calculation of nickel and copper atomic valencies in crystalline oxides

A new quantum chemical definition is proposed of the full atomic valence, V_A, taking into account both the covalent and ionic parts of the chemical bonds formed by atoms in molecules and crystals. The full atomic valencies, covalencies, and charges on atoms are calculated for nickel–oxygen crystalline compounds in the CNDO band theory approximation. A comparison of the chemical bonding in nickel and copper crystalline oxides is given. © 1994 John Wiley & Sons, Inc.     

Parametric analysis andab initio calculation of isotope shifts in rhenium I

The isotope shift in the arc spectrum of rhenium was studied in 12 lines for the highly enriched isotopes¹⁸⁵Re and¹⁸⁷Re by means of a photoelectric recording Fabry-Perot spectrometer with digital data processing. The observed shifts together with results from earlier studies were analyzed by means of the parametric method. The field shift difference between the terms 5d ⁶(⁵ D)6s ⁶ D and⁴ D was found to be 40 (5) mK, showing the influence of second-order effects. The parameterz _5d , displaying the magnitude of spin-dependent effects in 5d ⁶6s, was found to be 1.3 (8) mK. The experimental data are compared with results from non-relativistic Hartree-Fock calculations. The calculated electron densities describe the measured isotope shifts with good accuracy.     

Structures, energetics and vibrational frequency shifts of hydrated pyrimidine

More than 70 unique micro-hydrated structures of pyrimidine, ranging in size from 1 to 7 water molecules, have been characterized with the B3LYP density functional and the 6-311++G(2df,2pd) triple-ζ split-valence basis set. Explicitly correlated MP2-F12 single-point computations were performed on each structure with a correlation consistent triple-ζ basis set to estimate the relative and dissociation energies at the MP2 complete basis set (CBS) limit. Many of these new structures have significantly lower energies than those previously reported (by as much as 12.66 kcal?mol(-1)). For clusters with 1 and 2 water molecules, the MP2-F12 relative and dissociation energies are virtually identical to the corresponding CCSD(T)-F12 values. As the number of hydrating waters increases, the structures in which the water molecules are clustered together at one of the N atoms have lower energies than those where the water molecules are more distributed around the pyrimidine ring. Micro-hydrated structures that effectively extend the low-energy hydrogen-bonding motifs to both sides of the ring, as would be expected in the bulk phase, reproduce the experimentally observed vibrational frequency shifts of ν(1) and ν(8b) in very dilute aqueous pyrimidine solutions to within 1 cm(-1) . Micro-hydrated structures of pyrimidine in which water molecules are clustered together have lower energies than structures in which the water molecules are more evenly spread around the pyrimidine ring.     

Charge transfer and OH vibrational frequency red shifts in nitrate-water clusters

A theoretical study of charge transfer (CT) characteristics in nitrate (NO3(-)) anion-water complexes is presented, together with those for the halides, F-, Cl-, and Br-, for comparison. The relation between the vibrational frequency red shifts of the hydrogen (H)-bonded OH stretches and CT from the anion to the water molecule, established in previous work for the one-water complexes of the halides, is studied for both the one- and six-water nitrate complexes and is extended to the six-water case for the halides. In NO3(-) x H2O, the water molecule receives about as much charge as that in Br- x H2O. In a result consistent with aqueous phase infrared experiments [Bergstr?m, P. A.; Lindgren, J.; Kristiansson, O. J. Phys. Chem. 1991, 95, 8575-8580], the CT and OH red shift in NO3(-) x 6 H2O are found to be smaller than those for all of the six-water halide complexes, despite the presence of three H-bonding sites. The inability of the nitrate anion to effect substantial CT lies in the preservation of the pi-system being energetically favored over charge localization and enhancement of the strengths of the multiple H-bonds.     

Modification of the CO2 surface tension calculation model under low-temperature and high-pressure condition

Surface tension is an important thermodynamic parameter. In researching the removal mechanism of CO₂ in natural gas in supersonic expansion process, the most basic and important task is to calculate the surface tension of CO₂ under low-temperature and high-pressure condition. In this paper, a comparative study on the relevant calculation methods is carried out and the computational method applied to simulate the phase transition of CO₂ supersonic condensation is selected. On this basis, the CO₂ surface tension calculation model is modified and the calculation method, by using the piecewise function, is proposed. The results show that the average deviation of the piecewise function is only 0.95%, which is lower than the deviation of any single correlation. It can achieve an accurate prediction of the surface tension of the liquid CO₂.     

Semiclassical calculation of VV and VT rate coeffecients in CO

We have calculated 66 rate constants for vibration-vibration (V-V) and vibration-translation/rotation (V-T/R) energy transfer in CO by using a semiclassical collision model. Extensive comparison with experimental data and more approximate theoretical predictions is carried out.     

Low - frequency raman modes in crystalline chain molecules

Low - frequency Raman modes of substituted derivatives of n - alkanes and oligo(oxyethylene)s are discussed. The major features in these modes arise from whole molecule longitudinal vibrations. The effects of end group, chain length and temperature on the frequencies of these modes are described. The frequencies of the longitudinal vibrations are interpreted in terms of chain models.