DFT calculations with the symmetrized kohn–sham formalism for the electronic structure of the high-energy states of nitrogen dioxide

Quantum-chemical calculations of the electronic structure of the high-energy states of NO₂ were performed by the density functional method with symmetrized Kohn–Sham formalism. The results from the DFT calculation of the NO₂^* NO_2^* excited states agree well with experimental data and ab initio calculations. The reactivity of the long-lived excited state NO₂^*( [(C)\tilde]²A" ) NO_2^*\left( {{{\tilde{C}}^2}A'} \right) during photochemical conversion to NO₃ was investigated.     

S1←S0 vibronic spectra and the vapor-state molecular structure of propanal and 2-methylpropanal

The vapor-state absorption spectra have been recorded for propanal PA and 2-methylpropanal MP with path lengths up to 120 m. The initial points in the S₁S₀ electronic transitions have been identified together with various fundamental vibrational frequencies of the PA and MP conformers. They contain nonplanar aldehyde groups in the S₁ states with inversion potential barriers of about 600 cm^–1. The parameters of the internal-rotation potential functions in the S₁ states have been determined, and the corresponding potential functions in the S₀ states have been refined.Chemical Faculty, Lomonosov Moscow University. Translated from Zhurnal Strukturnoi Khimii, Vol. 34, No. 1, pp. 20–25, January–February, 1993.     

How accurate is the density functional theory combined with symmetry-adapted perturbation theory approach for CH-pi and pi-pi interactions? A comparison to supermolecular calculations for the acetylene-benzene dimer

Five different orientations of the acetylene-benzene dimer including the T-shaped global minimum structure are used to assess the accuracy of the density functional theory combined with symmetry adapted perturbation theory (DFT-SAPT) approach in its density-fitting implementation (DF-DFT-SAPT) for the study of CH-pi and pi-pi interactions. The results are compared with the outcome of counterpoise corrected supermolecular calculations employing second-order M?ller-Plesset (MP2), spin-component scaled MP2 (SCS-MP2) and single and double excitation coupled cluster theory including perturbative triple excitations (CCSD(T)). For all considered orientations MP2 predicts much deeper potential energy curves with considerably shifted minima compared to CCSD(T) and DFT-SAPT. In spite of being an improvement over the results of MP2, SCS-MP2 tends to underestimate the well depth while DFT-SAPT, employing an asymptotically corrected hybrid exchange-correlation potential in conjunction with the adiabatic local density approximation for the exchange-correlation kernel, is found to be in excellent agreement with CCSD(T). Furthermore, DFT-SAPT provides a detailed understanding of the importance of the electrostatic, induction and dispersion contributions to the total interaction energy and their repulsive exchange corrections.     

What is wise in the production of 99Mo? A comparison of eight possible production routes

The present paper addresses eight possible routes of producing ⁹⁹Mo, and discusses both yield and ⁹⁹Mo specific activities (SA) in the context of anticipated worldwide demand. Target dimensions are modelled by considering both limits set by cooling and by inside-target radiation attenuation characteristics. Energy deposition profiles are set up by MCNP6, reaction probabilities are taken from TALYS/TENDL and JANIS codes, and both are used in arriving at the produced ⁹⁹Mo. The outcomes suggest that U neutron-fission may remain one of the most relevant and efficient means of producing ⁹⁹Mo at the world-demand level, but that within this domain new developments may surface, such as ADSR or AHR production modes. Accelerator-based ⁹⁹Mo production is discussed as asking for developments in both target cooling and new concepts in post-EOB upgrading of ⁹⁹Mo SA, and/or new concepts for ⁹⁹Mo/^99mTc-generators, the latter possibly in both volumes (mass) and ⁹⁹Mo capacities.     

Does the choice of the crystal structure influence the results of the periodic DFT calculations? A case of glycine alpha polymorph GIPAW NMR parameters computations

Glycine is a common amino acid with relatively complex chemistry in solid state. Although several polymorphs (α, β, δ, γ, ε) of crystalline glycine are known, for NMR spectroscopy the most important is a polymorph, which is used as a standard for calibration of spectrometer performance and therefore it is intensively studied by both experimental methods and theoretical computation. The great scientific interest in a glycine results in a large number of crystallographic information files (CIFs) deposited in Cambridge Structural Database (CSD). The aim of this study was to evaluate the influence of the chosen crystal structure of α glycine obtained in different crystallographic experimental conditions (temperature, pressure and source of radiation of α glycine) on the results of periodic DFT calculation. For this purpose the total of 136 GIPAW calculations of α glycine NMR parameters were performed, preceded by the four approaches (“SP”, “only H”, “full”, “full+cell”) of structure preparation. The analysis of the results of those computations performed on the representative group of 34 structures obtained at various experimental conditions revealed that though the structures were generally characterized by good accuracy (R < 0.05 for most of them) the results of the periodic DFT calculations performed using the unoptimized structures differed significantly. The values of the standard deviations of the studied NMR parameters were in most cases decreasing with the number of optimized parameters. The most accurate results (of the calculations) were in most cases obtained using the structures with solely hydrogen atoms positions optimized. © 2018 Wiley Periodicals, Inc.     

Analysis of the vibronic structure of the 1A1g → 1B3g, 1B2u transition in biphenyl -h10 and -d10

The absorption spectra of biphenyl-h₁₀ and -d₁₀ crystals in the region of the ¹A_1g → 1B_3g, ¹B_2u transitions are interpreted in terms of vibronic coupling of the two closely spaced electronic states by six b_1u vibrations.     

Can undoped calcium tetraborides exist? An answer from the comparison of its density functional theory electronic structure with that of rare-earth metal tetraboride

Periodic density functional theory calculations are used to discuss the existence of metal tetraborides MB4 with divalent metals. Tetraborides which contain metal atoms inserted in a three-dimensional boron network made of B6 octahedra and B2 dumbbells exhibit a pseudo energy gap for a count of 60 valence electrons per M4(B6)2(B2)2 formula unit. Such a count satisfies the stability electron requirement for B6(2-) (20 electrons) octahedra and B2(2-) (8 electrons) units and allows the filling of two supplementary low-lying bands deriving from the valence metallic d atomic orbitals. This favored electron count is not reached for CaB4 which is then formally deficient by one electron per metal atom. This indicates that CaB4 is unlikely to exist without n-doping.     

Which electrospray-based ionization method best reflects protein-ligand interactions found in solution? A comparison of ESI,nanoESI, and ESSI for the determination of dissociation constants with mass spectrometry

We present a comparison of three different electrospray-based ionization techniques for the investigation of noncovalent complexes with mass spectrometry. The features and characteristics of standard electrospray ionization (ESI), chip-based nanoESI, and electrosonic spray ionization (ESSI) mounted onto a hybrid quadrupole time-of-flight mass spectrometer were compared in their performance to determine the dissociation constant (KD) of the model system hen egg white lysozyme (HEWL) binding to N,N',N'-triacetylchitotriose (NAG3). The best KD value compared with solution data were found for ESSI, 19.4 +/- 3.6 microM. Then, we determined the KDs of the two nucleotide binding sites of adenylate kinase (AK), where we obtained KDs of 2.2 +/- 0.8 microM for the first and 19.5 +/- 8.0 microM for the second binding site using ESSI. We found a weak charge state dependence of the KD for both protein-ligand systems, where for all ionization techniques the KD value decreases with increasing charge state. We demonstrate that ESSI is very gentle and insensitive to instrumental parameters, and the KD obtained is in good agreement with solution phase results from the literature. In addition, we tried to determine the KD for the lymphocyte-specific kinase LCK binding to a kinase inhibitor using nanoESI due to the very low amount of sample available. In this case, we found KD values with a strong charge state dependence, which were in no case close to literature values for solution phase.     

Analysis of coupled cluster methods. II. What is the best way to account for triple excitations in coupled cluster theory?

Summary Various coupled cluster (CC) and quadratic CI (QCI) methods are compared in terms of sixth, seventh, eighth, and infinite order Møller-Plesset (MPn, n=6, 7, 8, ) perturbation theory. By partitioning the MPn correlation energy into contributions resulting from combinations of single (S), double (D), triple (T), quadruple (Q), pentuple (P), hextuple (H), etc. excitations, it has been determined how many and which of these contributions are covered by CCSD, QCISD, CCSD(T), QCISD(T), CCSD(TQ), QCISD(TQ), and CCSDT. The analysis shows that QCISD is inferior to CCSD because of three reasons: a) With regard to the total number of energy contributions QCI rapidly falls behind CC for largen. b) Part of the contributions resulting from T, P, and higher odd excitations are delayed by one order of perturbation theory. c) Another part of the T, P, etc. contributions is missing altogether. The consequence of reason a) is that QCISD(T) covers less infinite order effects than CCSD does, and QCISD(TQ) less than CCSD(T), which means that the higher investment on the QCI side (QCISD(T) :O(M ⁷), CCSD :O(M ⁶), QCISD(TQ) :O(M ⁸), CCSD(T) :O(M ⁷),M: number of basis functions) does not compensate for its basic deficiencies. Another deficiency of QCISD(T) is that it does not include a sufficiently large number of TT coupling terms to prevent an exaggeration of T effects in those cases where T correlation effects are important. The best T method in terms of costs and efficiency should be CCSD(T).     

A comparison of low and high activity precatalysts: Do the calculated energy barriers during the self‐metathesis reaction of 1‐Octene correlate with the precatalyst metathesis activity?

The self‐metathesis reaction of 1‐octene with several well‐known Grubbs‐type precatalysts and the new Z‐selective Grubbs precatalyst were studied with molecular modeling. The obtained Gibbs‐free energy values for all the steps during the productive metathesis of 1‐octene were compared to the values obtained for some low catalytic activity precatalysts. Determining how the Gibbs‐free energy values of highly active precatalysts compare to that of low catalytic activity precatalysts gave a deeper insight into the mechanism. The questionable correlation of the theoretically observed trends with those obtained experimentally does point to the need to be very cautious when making assumptions from theoretical results without a sufficiently large dataset. © 2014 Wiley Periodicals, Inc.     

Comparison between the loading capacities of columns packed with partially and totally porous fine particles. What is the effective surface area available for adsorption?

The adsorption isotherms of phenol, caffeine, insulin, and lysozyme were measured on two C(18)-bonded silica columns. The first one was packed with classical totally porous particles (3 microm Luna(2)-C(18)from Phenomenex, Torrance, CA, USA), the second one with shell particles (2.7 microm Halo-C(18) from Advanced Materials Technology, Wilmington, DE, USA). The measurements were made at room temperature (T=295+/-1K), using mainly frontal analysis (FA) and also elution by characteristic points (FACP) when necessary. The adsorption energy distributions (AEDs) were estimated by the iterative numerical expectation-maximization (EM) procedure and served to justify the choice of the best adsorption isotherm model for each compound. The best isotherm parameters were derived from either the best fit of the experimental data to a multi-Langmuir isotherm model (MLRA) or from the AED results (equilibrium constants and saturation capacities), when the convergence of the EM program was achieved. The experiments show than the loading capacity of the Luna column is more than twice that of the Halo column for low-molecular-weight compounds. This result was expected; it is in good agreement with the values of the accessible surface area of these two materials, which were calculated from the pore size volume distributions. The pore size volume distributions are validated by the excellent agreement between the calculated and measured exclusion volumes of polystyrene standards by inverse size exclusion chromatography (ISEC). In contrast, the loading capacity ratio of the two columns is 1.5 or less with insulin and lysozyme. This is due to a significant exclusion of these two proteins from the internal pore volumes of the two packing materials. This result raises the problem of the determination of the effective surface area of the packing material, particularly in the case of proteins. This area is about 40 and 30% of the total surface area for insulin and for lysozyme, respectively, based on the pore size volume distribution validated by the ISEC method. The ISEC experiments showed that the largest and the smallest mesopores have rather a cylindrical and a spherical shape, respectively, for both packing materials.     

Application of the impulse oscillation model for modelling the formation of peroxocarbonates via carbon dioxide reaction with dioxygen transition metal complexes: A comparison with the experimental results obtained for Rh(η2-O2)ClP3 [P=phosphane ligand]

The reaction of CO₂ with (η²-dioxygen)-transition metal complexes to give peroxocarbonates has been modelled using the Impulse Oscillation Model (IOM).¹ In accordance with our experimental findings concerning the reactivity of P₃ClRh(η²-O₂) (P=phosphane ligand) complexes towards carbon dioxide, application of the model to this reaction shows that the insertion of carbon dioxide into the OO bond is the preferred pathway. In fact, the probability for CO₂ insertion into the OO bond equals maximum to 0.98 while into the M–O bond equals to 0.02. The concordance of calculated and experimental stretching frequencies indicates the possibility of identifying, through the vibration modes, proper ligands and metal systems that behave as selective catalysts at molecular level.     

A simple model for the band structure and D.C. conductivity of an infinite CO···H?N chain perpendicular to the protein backbone

The¹ Hartree–Fock crystal orbital (CO) method in its linear combination of atomic orbitals form was applied to determine the band structure of histone proteins taking 0.041e charge transfer per nucleotide base from the PO groups of poly(guanilic acid) to the arginine, and lysine side chains in histones (see text). Assuming that there are infinite COs, perpendicular to the main chain, formed by the amide groups of one segment of the protein chain bound together by H‐bonds with the C?O groups of another segment of the chain, we have calculated the band structure. From this, we have determined the mobility using the deformation potential approximation. Multiplying this with the mobile electron concentration due to the charge transfer between the PO groups of DNA and the positive side chains in histones, we have obtained for the direct current (D.C.) electron conductivity σ_fib = 1.07 × 10^?9 Ω^?1 cm for a single fiber and after division by the cross‐section of 9.10 × 10^?16 cm², σ_spec = 1.18 × 10⁶ Ω^?1 cm^?1 for the specific conductivity. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

What is the best bonding model of the (σ-H-BR) species bound to a transition metal? Bonding analysis in complexes [(H)2Cl(PMe3)2M(σ-H-BR)] (M = Fe, Ru, Os)

Density Functional Theory calculations have been performed for the σ-hydroboryl complexes of iron, ruthenium and osmium [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] (M = Fe, Ru, Os; R = OMe, NMe(2), Ph) at the BP86/TZ2P/ZORA level of theory in order to understand the interactions between metal and HBR ligands. The calculated geometries of the complexes [(H)(2)Cl(PMe(3))(2)Ru(HBNMe(2))], [(H)(2)Cl(PMe(3))(2)Os(HBR)] (R = OMe, NMe(2)) are in excellent agreement with structurally characterized complexes [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))], [(H)(2)Cl(P(i)Pr(3))(2)Os{σ-H-BOCH(2)CH(2)OB(O(2)CH(2)CH(2))}] and [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))]. The longer calculated M-B bond distance in complex [(H)(2)Cl(PMe(3))(2)M(σ-H-BNMe(2))] are due to greater B-N π bonding and as a result, a weaker M-B π-back-bonding. The B-H2 bond distances reveal that (i) iron complexes contain bis(σ-borane) ligand, (ii) ruthenium complexes contain (σ-H-BR) ligands with a stretched B-H2 bond, and (iii) osmium complexes contain hydride (H2) and (σ-H-BR) ligands. The H-BR ligands in osmium complexes are a better trans-directing ligand than the Cl ligand. Values of interaction energy, electrostatic interaction, orbital interaction, and bond dissociation energy for interactions between ionic fragments are very large and may not be consistent with M-(σ-H-BR) bonding. The EDA as well as NBO and AIM analysis suggest that the best bonding model for the M-σ-H-BR interactions in the complexes [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] is the interaction between neutral fragments [(H)(2)Cl(PMe(3))(2)M] and [σ-H-BR]. This becomes evident from the calculated values for the orbital interactions. The electron configuration of the fragments which is shown for C in Fig. 1 experiences the smallest change upon the M-σ-H-BR bond formation. Since model C also requires the least amount of electronic excitation and geometry changes of all models given by the ΔE(prep) values, it is clearly the most appropriate choice of interacting fragments. The π-bonding contribution is 14-22% of the total orbital contribution.     

The Liquid Junction Potential in Potentiometric Titrations. XII. The Calculation of Potentials for Emf Cells with Liquid Junctions, of the Type, AY | AY + A2MoO4+HY, Involving the Formation of Iso-Polymolybdates in the Range ?log?10[H+]��7, at [A+]=C mol?L?1, Constant, and 25?��C

Equations are derived, in a general form, and valid in the range 0.5??C??3 mol?L^?1, for the calculation of the total potential anomalies (??E _H) for emf cells where the formation of iso-polymolybdates takes place, according to the equilibria: $$p \mathrm{H}^{+} (h) + q \mathrm{MoO}_{4}^{2 -} (b)\rightleftharpoons [(\mathrm{H}^{+})_{p}(\mathrm{MoO}_{4}^{2-})_{q} ] ^{p - 2q} (cpx _{pq})$$ by measuring [H⁺]=h, in NaClO₄ ionic medium (A⁺, Y^?) at [Na⁺]=3 mol?L^?1. The total cell emf (E _H), can be defined as: $$E_{\mathrm{H}} = E_{\mathrm{0H}} + g \log_{10} h + g\log_{10} f_{\mathrm{HTS}2} +E_{\mathrm{D}} + E_{\mathrm{D}f}$$ where: E _0H is an experimental constant, E _D+E _Df =E _J, the classical liquid junction potential, and glog?₁₀ f _JTS2+E _D+E _Df =??E _H. Here, $\mathrm{MoO}_{4}^{2 -}$ is the central ??metal ion??, E _D is the ideal diffusion potential (Hendersson equation), E _Df is the contribution of the activity coefficients to E _D. f _HTS2 denotes the activity coefficient of the H⁺ ions in the terminal solution TS2. The investigations of this system made by Sasaki and Sillén are critically analyzed. Some emf cells are supposed for the determination of the interaction coefficients involved. All calculations are valid at 25?°C. The revised equilibrium constants are presented in Table 14.     

Search for a model to describe the specific adsorption of anions A? in Ga/[N-Methylformamide + mc KCl + (1 ? m)c KClO4] Systems, where KA is KCl, KBr, or KI

The adsorption parameters for systems Ga/[NMF + 0.1m M KCl + 0.1(1 ? m) M KClO₄], Ga/[NMF + 0.1m M KBr + 0.1(1 ? m) M KClO₄], and Ga/[NMF + 0.1m M KI + 0.1(1 ? m) M KClO₄] are calculated by using the regression analysis of the adsorption potential shift vs. electrode charge dependences for the following molar fractions m of the surface-active anion: 0.05, 0.1, 0.2, 0.5, and 1 within the framework of two models. The models are based on the Frumkin isotherm with the free adsorption energy dependent on the electrode charge, of which one model takes into account the diffuse layer and the other ignores it. It is shown that for electrode charges q ?? 16 ??C/cm², both models provide equal accuracy; however, for higher q, preference should be given to the model that takes into account the contribution of the double layer diffuse part.