Fragmentation at sp2 carbon atoms in fragment molecular orbital method

In the fragment molecular orbital (FMO) method, a given molecular system is usually fragmented at sp³ carbon atoms. However, fragmentation at different sites sometimes becomes necessary. Hence, we propose fragmentation at sp² carbon atoms in the FMO method. Projection operators are constructed using sp² local orbitals. To maintain practical accuracy, it is essential to consider the three-body effect. In order to suppress the corresponding increase of computational cost, we propose approximate models considering local trimers. Numerical verification shows that the present models are as accurate as or better than the standard FMO2 method in total energy with fragmentation at sp³ carbon atoms.     

Ionizing collisions of potassium atoms with molecules: Excitation energy of the product molecular ion

For processes of the type K + M

K⁺ + M^? at eV collision energies, measurements are reported of the population of excited states of the product negative ions. For M = Br₂ and SF₆ only a small excitation (0.5 – 3 eV) is found. For M = O₂, the products can be excited up to higher energies (? 5 eV); this is ascribed to a second electronic channel of the process.     

Stabilization of molecular atoms

We demonstrate the possibility of stabilizing the motion of ion-pair states through the use of external electric and magnetic fields. In conjunction with the Coulomb force, these fields can be engineered so as to lead to the creation of outer equilibrium points which can support non-spreading coherent wavepackets and long-lived states. Specific application is made to the H(+)-H- ion pair, recently investigated using threshold ion-pair production spectroscopy (TIPPS).     

Mills–Nixon effect in heteroanalogs of cyclopropabenzene

Structural properties of cyclopropabenzene and its heteroanalogs are studied at the SCF 6-31G level of theory. It is found that the Mills–Nixon (MN ) type of localization within the benzene ring is present in these systems. The origin of the bond fixation lies in rehybridization at the carbon junction atoms. π-electron bond orders usually follow changes within the sigma framework but can be misleading sometimes. It is shown that a judicious choice of heteroatoms can considerably enhance the MN effect. A refined and better definition of the MN effect is offered. Finally, present calculations and analysis of the results in terms of hybridization model and π-bond orders strongly indicate that experimental ⁴J(H? C? C? Me) proton–proton spin–spin couplings over four bonds can be used in identification of the MN effect only with extreme caution.     

Interaction of low-energy ions and atoms of light elements with a fluorinated carbon molecular lattice

The mechanism of interaction of low-energy atoms and ions of light elements (H, H+, He, Li, the kinetic energy of the particles 2-40 eV) with C6H6, C6F12, C60, and C60F48 molecules was studied by ab initio MD simulations and quantum-chemical calculations. It was shown that starting from 6 A from the carbon skeleton for the "C6H6 + proton" and "C60 + proton" systems, the electronic charge transfer from the aromatic molecule to H+ occurs with a probability close to 1. The process transforms the H+ to a hydrogen atom and the neutral C6H6 and C60 molecules to cation radicals. The mechanism of interaction of low-energy protons with C6F12 and C60F48 molecules has a substantially different character and can be considered qualitatively as the interaction between a neutral molecule and a point charge. The Coulomb perturbation of the system arising from the interaction of the uncompensated proton charge with the Mulliken charges of fluorine atoms results in an inversion of the energies of the electronic states localized on the proton and on the C6F12 and C60F48 molecules and makes the electronic charge transfer energetically unfavorable. On the different levels of theory, the barriers of the proton penetration for the C6F12 and C60F48 molecules are from two to four times lower than those for the corresponding parent systems (C6H6 and C60). The penetration barriers of the He atom and Li+ ion depend mainly on the effective radii of the bombarding particles. The theoretical penetration and escaped barriers for the "Li+ + C60" process qualitatively explain the experimental conditions of synthesis of the Li@C60 complex.     

Pseudopotentials for hybridized carbon atoms

Pseudopotentials for hybridized atoms are extracted and combined. The study focuses on sp² carbon atoms and their combination to give rise to a π electronic system. As electrons of interest are treated explicitly, any ab initio method can be used, thus, configuration interaction methods and time‐dependent density functional theory are used and compared. All electron and pseudopotential calculations are in good agreement for electronic transition spectroscopy (0.2 eV difference), geometrical parameters (error of 0.8 pm), and reaction energies. © 2012 Wiley Periodicals, Inc.     

On the nature of bonds between carbon atoms

The combined effect of conjugation and van der Waals' interaction has been calculated for carbon sp²-sp² single bonds of different lengths and for different molecular conformations. The bond shortening effect of conjugation is found to be comparable to that of hybridization. The attractive van der Waals' interaction, on the other hand, is always found to be small. It seems thus most improbable that this interaction should be the cause of the planarity of butadiene.     

Generation of iodobenzoborirene, a boraaromatic cyclopropabenzene derivative

Iodobenzoborirene is obtained photochemically (lambda = 308 nm) from diiodophenylborane by elimination of HI in solid argon at 10 K.     

Conversion of kinetic energy to internal energy in the 2-pentanone molecular ion at threshold in low-energy collisions with helium target atoms

Values of the threshold kinetic energy for formation of m/z 58 and m/z 43 from 2-pentanone molecular ion after collisional activation (CA) with He were studied in a hybrid tandem quadrupole system. These values indicate that the fraction of kinetic energy converted to internal energy and available for fragmentation is 0.14–0.25. Onset of conversion to internal energy through an electronically excited state was observed at 2.0 eV. Uses of He and heavier gases as collision gases in low-energy CA are projected to differ, He being used to screen classes of compounds and heavier gases to provide more complete structural information for ions.     

Keto-to-enol isomerization in the molecular ion of dimethylmethylphosphonate

A mechanism for keto-to-enol isomerization in dimethylmethylphosphonate (DMMP) has been proposed based on deuterium-labeling studies, a model compound and thermodynamic data. An electron ionization study of H/D exchange occurring in CD₃-labeled DMMP suggests that rapid keto-to-enol isomerization occurs in the ion source and a reaction mechanism based on sequential 1,4-H migrations rather than by the direct 1,3-H transfer or by sequential 1,2-H migrations is proposed. The examination of the mass-analyzed ion kinetic energy/collision-induced dissociation spectrum of the methylphosphonic acid molecular ion suggests that keto-to-enol isomerization does not occur for this species and that 1,2- and 1,3-H migrations are not favored. Available thermodynamic data were employed to construct a potential energy surface for keto-to-enol isomerization of the DMMP molecular ion. The thermodynamic data show that the energy barrier to isomerization is below the internal energy required for decomposition of the DMMP molecular ion. Additionally, the ΔH_f° for the intermediate and enolic isbmers are shown to be significantly less than the ΔH_f° for the keto form of the DMMP molecular ion.     

Motion of gold atoms on carbon in the aberration-corrected STEM.

The movement of heavy atoms on a thin carbon substrate is readily observed using a sub-Angstrom electron probe. The observed movement is consistent with an electron beam activation mechanism whereby atoms are occasionally detached from bonding sites, allowing rapid diffusion to new sites that may be quite far from the original. The bonding sites are most often observed to lie at defects, steps, and other asperities in the substrate. Formation of three-dimensional clusters can occur during diffusion of several isolated atoms. Coalescence and dissolution of larger clusters and islands both occur under varying observation conditions, but island coalescence appears most probable for islands that are greater than 2 nm in size.     

Recombination of carbon monoxide and oxygen atoms

The recombination of carbon monoxide and oxygen atoms was studied in reflected shock waves in H₂:O₂:CO:Ar = 0.1:1:24:75 with 1300 < T₅ 2200 K and 2 < P₅ < 4 atm. Reaction progress was monitored by observations of the carbon monoxide flame spectrum near 435 nm and carbon dioxide thermal emission near 4.2 μm. Data analysis was accomplished with the aid of computer modeling using a 27-reaction mechanism. Computer modeling experiments also showed that these measurements were sensitive primarily to the rate of the reaction CO + O + M = CO₂ + M and only slightly sensitive to the rates of other reactions. The best fit to the data was achieved with a rate constant for this reaction of 7.7 × 10^?35 exp[19 kJ/RT] cm⁶ s for the temperature range of these experiments. Correlation of this result and previous data covering the temperature range 250 < T < 11,000 K confirms that this recombination reaction is governed by a nonadiabatic curve crossing with an activation barrier of about 20 kJ and subsequent deactivation of a singlet CO₂ molecule.     

On the origin of the 22 and 23 carbon atoms in strychnine

The results of 1-[¹⁴C]-sodium acetate feeding experiments with Strychnos nux vomica L. have shown that the C-atoms 22 and 23 of strychnine are very probably acetate derived.     

Intercalation of multiple carbon atoms between the carbonyls of alpha-diketones

The reaction of open-chain or cyclic alpha-diketones with specific omega-alkenyl organometallics leads readily under the proper conditions to 1,2-diols bonded to terminal olefinic chains. With 1-phenyl-1,2-propanedione, biacetyl, and cyclohexane-1,2-dione, allylindation in aqueous THF proceeds readily at both adjacent carbonyls. For cyclododecane-1,2-dione, recourse must be made to allylmagnesium bromide for completing the second-stage condensation. Grignard reagents have also served well as reactants for biacetyl monoadducts. In contrast, monoallylated camphorquinone is reluctant to couple to Grignard reagents and reacts only when Barbier-type alkyllithium reactions are applied. The ring closing metatheses of these products have been examined. Where six-membered ring formation operates, cyclization can be performed directly on diols. When larger rings are involved, the diols will react only if structural preorganization capable of facilitating mutual approach of the two double bonds is at play. For this purpose, the prior conversion to a cyclic carbonate holds considerable utility. In the latter setting, saponification must precede the diol cleavage step which has been performed with lead tetraacetate. The latter reagent also exhibits the very beneficial effect of facilitating removal of ruthenium and phosphorus byproducts generated during the metathesis step. This chemistry conveniently lends itself to the controlled intercalation of multiple methylene groups between the carbonyl carbons of readily available alpha-diketones to deliver linear or cyclic products.     

Unrestricted Hartree-Fock functions for the carbon and fluorine atoms

An attempt to solve the Hartree-Fock equations for the (non-relativistic) carbon and fluorine atoms is reported. No constraints are placed on the minimisation of the parametrised energy function arising from the use of the finite expansion method within the single determinant model of atomic electronic structure except those implicit in the expansion method itself.     

Collision-induced dissociation of the phenylsilane molecular ion

The high-energy collision-induced dissociation of the phenylsilane molecular ion generated by electron ionization has been investigated using tandem mass spectrometry (MS/MS). It was observed that the dissociation of the molecular ion (M(+*)) occurs mainly via [M-H](+), [M-2H](+*), and [M-3H](+), followed by two consecutive losses of C(2)H(2). The structures of the precursors for the [M-CH(3)](+), [M-SiH](+), and [M-SiH(2)](+*) ions are proposed. The data suggest that the molecular ion undergoes rearrangements to several isomers prior to dissociation, including the ion containing a five-membered carbon ring. Reaction mechanisms are proposed for the dissociations via the isomeric molecular ions.     

Energy-dependent fragmentation of the p-ethyltoluene molecular ion

The p-ethyltoluene molecular ion fragments by loss of either the methyl group attached to the ring or the β-methyl of the ethyl group. Using specific isotopic labeling and charge exchange techniques the relative importance of the losses of the two methyl groups has been studied as a function of internal energy from metastable ions to ions of 7 eV internal energy. The ratio of loss of the β-methyl to loss of the ring-methyl increases from 3.4 for metastable ions to 6.7 for ions of 7 eV internal energy. This variation is interpreted in terms of an energy-dependent competition between fragmentation and hydrogen migration in a dimethylcy-cloheptatriene intermediate. In variable energy collision-induced dissociation studies the ratio of loss of the β-methyl to loss of the ring-methyl decreases with increasing collision energy. It is speculated that this different behavior is related to the differences in preparation of the molecular ions. Those subjected to collisional activation are prepared initially as ground-state ethyltoluene ions and are vibrationally excited upon collision and may fragment largely from the original structure. By contrast, in the charge exchange and electron impact experiments the molecular ions with sufficient energy to fragment are probably formed initially in electronically excited states and the rearrangement to the cycloheptatriene structure may be more facile in these excited states or during the internal conversion processes leading to vibrationally excited ground-state ions.     

The structure of the benzene molecular ion

The kinetic energy released by the [C₆H₆]^+. ion generated (i) by direct ionization of benzene and (ii) by charge-exchange of [C₆H₆]⁺⁺ suggests that the reactive form of the benzene molecular ion has an acyclic structure.     

Moment functions of the hydrogen molecular ion

The moment functions of H⁺₂ are computed for internuclear distances up to 5a₀ from the dipole osciliator strengths.