Quantum chemical calculations of stability constants: study of ligand effects on the relative stability of Pd(II)�Cpeptide complexes

Replacement of [Pd(H₂O)₄]²⁺ by cis-[Pd(en)(H₂O)₂]²⁺, [PdCl₄]^2?, and [Pd(NH₃)₄]²⁺ on the hydrolytic cleavage of the Ace-Ala-Lys-Tyr-Gly?CGly-Met-Ala-Ala-Arg-Ala peptide is theoretically investigated by using different quantum chemical methods both in the gas phase an in water solution. First, we carry out a series of validation calculations on small Pd(II) complexes by computing high-level ab initio [MP2 and CCSD(T)] and Density Functional Theory (B3LYP) electronic energies while solvent effects are taken into account by means of a Poisson-Boltzmann continuum model coupled with the B3LYP method. After having assessed the actual performance of the DFT calculations in predicting the stability constants for selected Pd(II)-complexes, we compute the relative free energies in solution of several Pd(II)?Cpeptide model complexes. By assuming that the reaction of the peptide with cis-[Pd(en)(H₂O)₂]²⁺, [Pd(Cl)₄]^2?, and [Pd(NH₃)₄]²⁺ would lead to the initial formation of the respective peptide-bound complexes, which in turn would evolve to afford a hydrolytically active complex [Pd(peptide)(H₂O)₂]²⁺ through the displacement of the en, Cl^?, and NH₃ ligands by water, our calculations of the relative stability of these complexes allow us to rationalize why [Pd(H₂O)₄]²⁺ and [Pd(NH₃)₄]²⁺ are more reactive than cis-[Pd(en)(H₂O)₂]²⁺ and [PdCl₄]^2? as experimentally found.     

Generalized electron number distribution functions: real space versus orbital space descriptions

The algebraic expressions previously derived to compute the electron number distribution functions (EDF) for exhaustive partitions of the physical space into sharp-boundary atoms are generalized to allow for the use of fuzzy atoms and orbital-based partitions. In some of the latter, the atomic overlap matrix required to obtain the EDF is analytical. This makes them attractive alternatives to other definitions, as the one based on the atomic basins of the quantum theory of atoms in molecules (QTAIM), which are more physically sound but also much more demanding computationally. We will compute the EDF for a series of test molecules using different fuzzy and orbital-based partitions and compare them to QTAIM EDF. The effects of electron correlation and the use of the core approximation on the EDF will also be explored.     

On the anomaly of the quasiclassical product distributions of the \hbox{OH} +\hbox{CO} \rightarrow\hbox{H} +\hbox{CO}_2 reaction

A grid empowered molecular simulator (GEMS) embodying in a single workflow the ab initio treatment of elementary chemical processes has been extended to four atom reactions. GEMS has been used to carry out a massive quasiclassical investigation for the $\hbox{OH} +\hbox{CO} \rightarrow\hbox{H} +\hbox{CO}_2$ reaction on the most recently proposed potential energy surface. The type of potential energy surface used and the possibility of running the simulations on the grid have allowed us to keep the error of the order of a few percent at all values of the collision energy and to estimate accurately the dependence of the reaction cross section on the collision energy. The accuracy of the calculations has allowed to unequivocally single out the fact that the calculated center-of-mass angular distribution is clearly isotropic and radically differs from the asymmetric forward?Cbackward structure obtained from the experiment. However, when the laboratory frame analogues are compared, the difference almost vanishes.     

A 3D-analysis of the Cl?�Cbenzene dimer solvation by Ar atoms

The solvation of the Cl^??Cbenzene (Cl^??CBz) aggregate by Ar atoms has been investigated employing molecular dynamics (MD) simulations. The gradual evolution from cluster rearrangement to solvation dynamics is discussed by considering ensembles of n (n = 1,...,30) Ar atoms around the Cl^??CBz clusters. The energetic of the solvated cluster is decomposed as a sum of pairs (including both the Ar?CAr and the Cl^??CAr terms), Cl^??CBz and Ar?CBz interactions and their relative contributions are analyzed as a function of the cluster size. The geometrical distribution of Ar atoms around Cl^??CBz is investigated in terms of radial distribution functions (RDF), bidimensional (2D) angular distributions and tridimensional (3D) probability densities. The variation on the spatial distribution of the Ar atoms around Cl^??CBz when the Ar number increases is investigated from a novel prospective, employing spherical coordinates of the solvent atoms within an inertial reference frame. Isomerization processes are also studied.     

Study of the interaction between aniline and CH3CN, CH3Cl and CH3F

A computational study of dimers formed by aniline and one or two CH₃X molecules, X being CN, Cl or F, was carried out to elucidate the main characteristics of the interacting systems. Two different structures were found for each of the dimers, depending on the relative location of the CH₃X molecule with respect to the NH₂ hydrogen atoms. The most stable complex is formed with acetonitrile, with a complexation energy amounting to ?27.0?kJ/mol. Methyl chloride and methyl fluoride form complexes with complexation energies amounting to ?18.1 and ?17.5?kJ/mol, respectively, though the structural arrangement is quite different for both structures. In most complexes, the leading contribution to the stabilization of the complex is dispersion, though the electrostatic contribution is almost as important. Three different minima were obtained for clusters containing two CH₃X molecules depending on the side they occupy with respect to the phenyl ring. The complexation energies for these structures amount to ?58.5, ?38.6 and ?36.3?kJ/mol for acetonitrile, methyl chloride and methyl fluoride, respectively.     

Monitoring of the electrochemical degradation of PEDOT films on gold using the bending beam method

Electrochemical and mechanical properties of thin poly(3,4-ethylenedioxythiophene) films deposited on gold have been investigated in aqueous sulfuric acid and sodium-sulfate solutions. It has been shown that at sufficiently positive electrode potentials, overoxidation of the polymer takes place. In some cases, only small changes could be observed in the shape of cyclic voltammograms taken in the “stability region??before and after overoxidation. In contrast to this, the impedance spectra recorded after overoxidation differed considerably from the impedance spectra of a freshly made electrode. Morphological changes of the polymer caused by overoxidation (degradation) could be detected by using the bending beam method.     

Novel titanium(iv) complexes with 2,4-di-tert-butyl-6-(1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl)phenol in ethene polymerization

Dinuclear (2) and mononuclear dichloride complexes (3) of titanium(iv) isopropoxide with a bidentate phenol alcohol ligand, viz., 2,4-di-tert-butyl-6-(1,1,1,3,3,3-hexafluoro-2-hydroxy-propan-2-yl)phenol, were obtained. The structures of the complexes were confirmed by X-ray diffraction. The dimeric structure of complex 2 is typical of alkoxy compounds and contains the bridging fragment Ti(??-OPrⁱ)₂Ti; the coordination polyhedron of the Ti atom is a distorted tetragonal pyramid. In complex 3, the Ti atom has a distorted octahedral environment made up of the O atoms of the ligand, the Cl atoms, and the O atoms of two coordinated propan-2-ol molecules. The catalytic properties of complexes 2 and 3 in ethene polymerization were studied with such promoters as polymethylaluminoxane (MAO), trimethylaluminum, triisobutylaluminum, diethylaluminum chloride, and Et₂AlCl-MgBu₂. Both the complexes were catalytically active (635 and 540 kg of polyethylene (PE)/(mol of Ti) h atm, respectively) only in the presence of the binary promoter Et₂AlCl-MgBu₂. The dichloride complexes obtained from a lithium or magnesium salt of the same ligand and TiCl₄ without separation from lithium and magnesium chlorides formed as by-products were catalytically active in the presence of MAO, Buⁱ ₃Al, and Me₃Al. For the catalytic system containing the dichloride complex and MgCl₂, the best promoter is Me₃Al (1082 kg of PE/(mol of Ti) h atm). The polymer obtained on all the catalytic systems is linear polyethylene characterized by high molecular weight (M_w = = 593900?C2000000 g mol^?1) and high polydispersity indices (M_w/M_n = 2.8?C15). Various conjectures were made about why lithium and magnesium chlorides have the promoting effects.