A direct transition state theory based analysis of the branching in NH2 + NO

A combination of high-level quantum-chemical simulations and sophisticated transition state theory analyses is employed in a study of the temperature dependence of the N2H + OH-->HNNOH recombination reaction. The implications for the branching between N2H + OH and N2 + H2O in the NH2 + NO reaction are also explored. The transition state partition function for the N2H + OH recombination reaction is evaluated with a direct implementation of variable reaction coordinate (VRC) transition state theory (TST). The orientation dependent interaction energies are directly determined at the CAS + 1 + 2/cc-pvdz level. Corrections for basis set limitations are obtained via calculations along the cis and trans minimum energy paths employing an approximately aug-pvtz basis set. The calculated rate constant for the N2H + OH-->HNNOH recombination is found to decrease significantly with increasing temperature, in agreement with the predictions of our earlier theoretical study. Conventional transition state theory analyses, employing new coupled cluster estimates for the vibrational frequencies and energies at the saddlepoints along the NH2 + NO reaction pathway, are coupled with the VRC-TST analyses for the N2H + OH channels to provide estimates for the branching in the NH2 + NO reaction. Modest variations in the exothermicity of the reaction (1-2 kcal mol-1), and in a few of the saddlepoint energies (2-4 kcal mol-1), yield TST based predictions for the branching fraction that are in satisfactory agreement with related experimental results. The unmodified results are in reasonable agreement for higher temperatures, but predict too low a branching ratio near room temperature, as well as too steep an initial rise.     

States on Orthomodular Posets of Decompositions

In Harding (Transactions of American Mathematical Society (1996) 348(5), 1839–1862), it was shown that the direct product decompositions of a set X naturally form an orthomodular poset Fact X. Here it is shown that Fact X has a state if and only if X is finite. An example is also given of a finite orthomodular poset that can be embedded into Fact X for X countable, but not for X finite.     

Glycerinanalyse

Ohne Zusammenfassung     

Coupled-cluster reference values for the GW27 and GW100 test sets for the assessment of GW methods

The vertical ionisation energies of the molecules of the GW27 (27 molecules) and GW100 (100 molecules) test sets are computed in a polarised triple-zeta-valence basis set in the framework of coupled-cluster theory with single, double, and non-iterative triple substitutions. The molecular geometries were kept fixed to those of the two test sets. To demonstrate the usefulness of the coupled-cluster reference values, they are compared with quasi-particle energies obtained in the G₀W₀ approximation for functionals commonly used in Kohn–Sham density-functional theory (DFT). Furthermore, an approximation is assessed, in which only exchange contributions are added to the DFT orbital energies.     

ESI-MS and thermal melting studies of nanoscale platinum(II) metallomacrocycles with DNA

The hydrophilic, long-chain diamine PEGda (O,O'-bis(2-aminoethyl)octadeca(ethylene glycol)), when complexed with cis-protected Pt(II) ions afforded water-soluble complexes of the type [Pt(N,N)(PEGda)](NO(3))(2) (N,N = N,N,N',N'-tetramethyl-1,2-diaminoethane (tmeda), 1,2-diaminoethane (en), and 2,2'-bipyridine (2,2'-bipy)) featuring unusual 62-membered chelate rings. Equimolar mixtures containing either the 16-mer duplex DNA D2 or the single-stranded D2a and [Pt(N,N)(PEGda)](2+) were analyzed by negative-ion ESI-MS. Analysis of D2-Pt(II) mixtures showed the formation of 1 : 1 adducts of [Pt(en)(PEGda)](2+), [Pt(tmeda)(PEGda)](2+) and the previously-described metallomacrocycle [Pt(2)(2,2'-bipy)(2){4,4'-bipy(CH(2))(4)4,4'-bipy}(2)](8+) with D2; the dinuclear species bound to D2 most strongly, consistent with its greater charge and aromatic surface area. D2 formed 1 : 2 complexes with the acyclic species [Pt(2,2'-bipy)(Mebipy)(2)](4+) and [Pt(2,2'-bipy)(NH(3))(2)](2+). Analyses of D2a-Pt(II) mixtures gave results similar to those obtained with D2, although fragmentation was more pronounced, indicating that the nucleobases in D2a play more significant roles in mediating the decomposition of complexes than those in D2, in which they are paired in a complementary manner. Investigations were also conducted into the effects of selected platinum(II) complexes on the thermal denaturation of calf thymus DNA (CT-DNA) in buffered solution. Both [Pt(2)(2,2'-bipy)(2){4,4'-bipy(CH(2))(6)4,4'-bipy}(2)](8+) and [Pt(2,2'-bipy)(Mebipy)(2)](4+) stabilized CT-DNA. In contrast, [Pt(tmeda)(PEGda)](2+) and [Pt(en)(PEGda)](2+) (as well as free PEGda) caused negligible changes in melting temperature (ΔT(m)), suggesting that these species interact weakly with CT-DNA.     

Structural consequences of the one-electron reduction of d4 [Mo(CO)2(eta-PhC[triple bond]CPh)Tp']+ and the electronic structure of the d5 radicals [M(CO)L(eta-MeC[triple bond]CMe)Tp'] {L = CO and P(OCH2)3CEt}

Reduction of [M(CO)2(eta-RC[triple bond]CR')Tp']X {Tp' = hydrotris(3,5-dimethylpyrazolyl)borate, M = Mo, X = [PF6]-, R = R' = Ph, C6H4OMe-4 or Me; R = Ph, R' = H; M = W, X = [BF4]-, R = R' = Ph or Me; R = Ph, R' = H} with [Co(eta-C5H5)2] gave paramagnetic [M(CO)2(eta-RC[triple bond]CR')Tp'], characterised by IR and ESR spectroscopy. X-Ray structural studies on the redox pair [Mo(CO)2(eta-PhC[triple bond]CPh)Tp'] and [Mo(CO)2(eta-PhC[triple bond]CPh)Tp'][PF6] showed that oxidation is accompanied by a lengthening of the C[triple bond]C bond and shortening of the Mo-C(alkyne) bonds, consistent with removal of an electron from an orbital antibonding with respect to the Mo-alkyne bond, and with conversion of the alkyne from a three- to a four-electron donor. Reduction of [Mo(CO)(NCMe)(eta-MeC[triple bond]CMe)Tp'][PF6] with [Co(eta-C5H5)2] in CH2Cl2 gives [MoCl(CO)(eta-MeC[triple bond]CMe)Tp'], via nitrile substitution in [Mo(CO)(NCMe)(eta-MeC[triple bond]CMe)Tp'], whereas a similar reaction with [M(CO){P(OCH2)3CEt}(eta-MeC[triple bond]CMe)Tp']+ (M = Mo or W) gives the phosphite-containing radicals [M(CO){P(OCH2)3CEt}(eta-MeC[triple bond]CMe)Tp']. ESR spectroscopic studies and DFT calculations on [M(CO)L(eta-MeC[triple bond]CMe)Tp'] {M = Mo or W, L = CO or P(OCH2)3CEt} show the SOMO of the neutral d5 species (the LUMO of the d4 cations) to be largely d(yz) in character although much more delocalised in the W complexes. Non-coincidence effects between the g and metal hyperfine matrices in the Mo spectra indicate hybridisation of the metal d-orbitals in the SOMO, consistent with a rotation of the coordinated alkyne about the M-C2 axis.     

Kohlenhydrate

Ohne Zusammenfassung