Floating spherical Gaussian orbital model study of some hydrogen-bridged systems: LiBeH3, LiBH4, LiCH5, and BeBH5

The floating spherical Gaussian orbital (FSGO ) method has been used to study the equilibrium geometries and electronic structures of some hydrogen-bridged systems containing lithium, beryllium, boron, and carbon. The predicted geometries are in good agreement with other theoretical estimates. The binding energies for these hydrogen-bridged systems are estimated and discussed. The FSGO total energies (E_FSGO ), for all systems studied here, are found to be well correlated to nuclear–nuclear repulsion (V_nn) and nuclear–electron attraction (V_ne) terms by a relation of the type E_FSGO =\documentclass{article}\pagestyle{empty}\begin{document}$ {\textstyle{3 \over 7}} $\end{document} (2 V_nn + V_ne).     

Floating spherical gaussian orbital (FSGO) studies with a model potential: some open-shell systems

A gaussian based model potential is used within the FSGO formalism to study a series of open-shell systems (e.g. LiH⁺, NaH⁺, Li⁺₂ and LiNa⁺). Results for calculated equilibrium geometries and dissociation energies are compared to the corresponding quantities from available all-electron ab initio studies and other more elaborate theoretical estimates. The overall agreement is quite satisfactory.     

The floating spherical gaussian orbital model and shape of B2H5 ion

The FSGO model has been used to make ab initio calculations of the geometry of B₂H ion. The results indicate that the acetylenic structure has the lowest energy (?43.881 a.u.) and the planar structure has the highest energy (?43.838 a.u.). The energy of the non-symmetric structure is only slightly higher (?43.879 a.u.) than that of the acetylenic one. Results of CNDO /2 calculations reported here also predict the acetylenic structure to be the most stable one.     

Floating spherical Gaussian orbital (FSGO) studies with a model potential: Application to two-valence-electron systems

A Gaussian based model potential is used within FSGO formalism to study a series of two-valence-electron diatomics (Li₂, Na₂, K₂, LiH, NaH, KH, MgH⁺, CaH⁺, LiNa, LiK and NaK) and triatomic ions (H₂Li⁺, H₂Na⁺, Li₂Na⁺, Na₂Li⁺, Li ₃ ⁺ , Na ₃ ⁺ , Li₂H⁺ and Na₂H⁺). Results for calculated equilibrium geometries, force constants, and energy changes for certain chemical reactions are compared to the corresponding quantities from available all-electronab initio studies and experimental results. The predicted results are generally satisfactory.Aided by grants to the University of North Carolina from the National Institute of Health and the National Science Foundation.     

Floating spherical Gaussian orbital model study of average electric polarisabilities and magnetic susceptibilities: Some aliphatic hydrocarbons

Floating spherical Gaussian orbital model is used to discuss the average electric polarisabilities and magnetic susceptibilities of a series of hydrocarbons. It has been noticed that the core contributions are negligibly small and these quantities (average electric polarisabilities and magnetic susceptibilities) can be well estimated from contributions localised on bond Gaussians.     

A floating spherical gaussian orbital model of molecular structure. XII. Analysis of energy terms affecting the geometry of the water molecule

The energy terms arising in the water calculation by the FSGO method are analyzed as a function of the bond angle in order to gain insight into the reasons for the particular equilibrium configuration. The analysis is made in terms of symmetrically orthogonalized orbitals so as to exclude three- and four-orbital electron repulsion terms.     

Absolute raman intensities of CH3I,CH2DI,CHD2I and CD3I. Experimental results

The absolute Raman intensities of methyl iodide and deuterated derivatives have been measured in the gas phase, with an experimental accuracy of ten percent. We report the frecuency independent scattering coefficients and depolarization ratios, as well as the Raman tensor invariants, squared mean polarizability and anisotropy, derived from them.     

A non-local pseudopotential in the FSGO model: Study of some organometallic systems

A non-local core pseudopotential has been used in the framework of floating spherical Gaussian orbital (FSGO ) model to study the equilibrium geometries and valence electronic structures of some organolithium and organoberyllium systems. The calculated equilibrium geometries, heats of hydrogenation, average electric polarizabilities, and magnetic susceptibilities are in good agreement with the results of the all-electron FSGO model calculations. Valence electron wave functions obtained here have been used to predict the valence electron Compton profiles (CP ) and electron momentum distributions (EMD ) of the systems studied. A good correlation has been shown among the peak height of the CP (J(0)), valence electron energy (E_v), and number of valence electrons (N_v).     

Orbital topology. I. A basic topological model for chemical systems,an orbital mapping technique,and analyses of model,thermal electrocyclic reactions

A topological model which provides a unifying framework for chemical reactions and molecular structure is proposed. Such basic concepts as overlap, orthogonality, reaction continuity, reaction reversibility, and orbital correspondence are incorporated into the model in a logical fashion. A chemical reaction pathway is regarded as a function that transforms a reactant topological space into its equivalent product space. The unique character usually ascribed to reactants, products, and their wavefunctions is superfluous. The model also allows considerable approximation of the wavefunctions and the reaction pathway without affecting the overall result. A simple orbital mapping technique consistent with the model which traces the transformation of orbitals using intermolecular overlaps of the orbitals is also proposed. The suitability of a given pathway (“allowed” or “forbidden”) can be deduced explicitly without invoking symmetry (or other) rules and without resorting to detailed calculation of reaction energy surfaces. The validity of the mapping procedure has been confirmed by several thermal electrocyclic reactions: the ring-opening isomerizations of substituted cyclopropyl cations, cyclopropyl anion, cyclopropanone, cyclobutene, benzocyclobutene, Dewar benzenes, and 1,3-cyclohexadiene. Orbital mapping with EHT and CNDO/2 MOs correctly predicts the reaction stereochemistry (conrotatory or disrotatory) in every case.     

An ab initio study of the CH3I photodissociation. I. Potential energy surfaces

The multireference spin-orbit (SO) configuration interaction (CI) method in its Lambda-S contracted SO-CI version is employed to calculate two-dimensional potential energy surfaces for the ground and low-lying excited states of CH3I relevant to the photodissociation process in its A absorption band. The computed equilibrium geometry for the X A1 ground state, as well as vibrational frequencies for the nu2 umbrella and nu3 symmetric stretch modes, are found to be in good agreement with available experimental data. The 3Q0+ state converging to the excited I(2P1/2o) limit is found to possess a shallow minimum of 850 cm(-1) strongly shifted to larger internuclear distances (RC-I approximately 6.5a0) relative to the ground state. This makes a commonly employed single-exponent approximation for analysis of the CH3I fragmentation dynamics unsuitable. The 4E(3A1) state dissociating to the same atomic limit is calculated to lie too high in the Franck-Condon region to have any significant impact on the A-band absorption. The computed vertical excitation energies for the 3Q1, 3Q0+, and 1Q states indicate that the A-band spectrum must lie approximately between 33,000 and 44,300 cm(-1), i.e., between 225 and 300 nm. This result is in very good agreement with the experimental findings. The lowest Rydberg states are computed to lie at >or=49,000 cm(-1) and correspond to the ...a(1)2n3a1(6sI) leading configuration. They are responsible for the vacuum ultraviolet absorption lines found experimentally beyond the A-band spectrum at 201.1 nm (49,722 cm(-1)) and higher.     

A computational exploration of some transnitrosation and thiolation reactions involving CH3SNO, CH3ONO and CH3NHNO

Nitric oxide (NO) is a biologically active species and its carrier molecules RXNO (X = S, O, NH) have drawn significant attention recently. In the present work, the CBS-QB3 level of theory was used to study the transnitrosation and thiolation reaction between MeXNO (X = S, O, and NH) molecules and three reactive forms of the methanethiol: the neutral molecule, MeSH, the anion, MeS-, and the radical, MeS . The transnitrosation and thiolation reactions between MeXNO and MeSH have the highest barriers, both with and without a molecule of water assisting. Reactions with MeS- proceed with much lower barriers, while reactions with radical MeS have the lowest barriers. Comparing the reactions of MeXNO (X = S, O, NH), both transnitrosation and thiolation are more favorable for X = S than X = O or NH.     

Deactivation of I(52P1/2) by CF3I,CH3I,C2H5I,and CH4

The technique of laser photolysis of alkyl and perfluoroalkyl iodides at 266 nm followed by time-resolved detection of the 1.3-μm emission from I^*(²P_1/2) has been used to measure the rate constants for deactivation of I^* by CH₃I, C₂H₅I, CF₃I, and CH₄. The recommended values are (2.76± 0.22) × 10^?13, (2.85 ± 0.40) × 10^?13, (3.5 ± 0.5) × 10^?17, and (7.52 ± 0.12) × 10^?14, respectively, in units of cm³ molecule^?1 S^?1.     

Production of organometallic polymers by the interfacial technique. I. Interfacial production of polyalkyloxysilanes and a study of some reaction variables

The first interfacial synthesis of polyalkyloxysilanes of the form where R′ = alkylene, and R″, R = alkyl or aryl is reported. It is found, in the range studied for the stirred systems, that as organic solvent viscosity and organic phase volume are increased, rate of polymer formation is decreased. Little difference in polymer formation rate is observed when the nature of the diol is varied, but considerable difference is noted when the nature of the organosilane is varied such that the most electropositive silane has the highest rate of polymer formation. Molecular weight is approximately constant as diol is changed but varies markedly when the silane is changed, so that the silane with the most bulky substance will give polymer with the lowest molecular weight.     

Competition between hydrogen abstraction and halogen displacement in the reaction of Br with CH3I, CH3Br, and CH3Cl

Sudden ozone depletion events in the marine boundary layer are associated with jumps in the CH3Br mixing ratio, but current models of atmospheric chemistry explain neither the ozone depletion nor the CH3Br spikes. We have used ab initio theory to predict the forward and reverse rate constants for the competing hydrogen abstraction and homolytic substitution (SH2) channels of the title reactions. Including the spin-orbit stabilization of the transition structures increases the rate constants by factors between 1.3 and 49. For the atmospherically relevant case of CH3I, our findings suggest that the hydrogen abstraction and homolytic substitution reactions are competitive. The predicted branching fraction to CH3Br is about 13%.     

Sulphur substituted organometallic compounds III. Reactions of Ph3SnCH2CH2SC6H4Me-p with some electrophilic reagents

Two distinct types of reactions of electrophiles, EN, with Ph₃SnCH₂CH₂SC₆H₄Me-p (I) have been established. Thus I₂ and HgCl₂ cleave the phenyltin bond: I + EN → Ph₂(N)SnCH₂CH₂SC₆H₄Me-p + PhE (E  I, N  I; E  HgCl, N  Cl) while from the reactions of Br₂ and MeI, as well as of ArSCl, as previously reported, ethylene is evolved: I + EN → Ph₃SnN + CH₂CH₂ + ESC₆H₄Me-p (E  Br, N  Br; E  Me, N  I)     

A molecular orbital analysis of Cu(I)-catalysed cyclopropanation using diazoalkanes with CH3 and CF3 substituents

The mechanism of cyclopropanation catalysed by Cu(I) complexes has been investigated by calculation using a series of diazoalkanes containing inductive electron donating (methyl) and withdrawing (CF3) substituents and a range of metal fragments (Cu+, [(DAB)Cu]+, ClCu and (triflate)Cu). Copper-diazoalkane complexes exist as an equilibrium of C- and N-bonded isomers. Catalysis occurs through lowering of the activation energy for rate determining C-N bond cleavage of the C-bonded isomer; this is most marked for (triflate)Cu. Direct reaction of the copper-carbene complex occurs to yield stable cupracyclobutanes in all but one case. Associative substitution of the cupracyclobutane by diazoalkane completes the catalytic cycle.     

An ab initio molecular orbital study of the grignard reagents CH3MgCl and [CH3MgCl]2: The Schlenk equilibrium

Ab initio molecular orbital calculations are used to study the modified Schlenk equilibrium: 2RMgCl (RMgCl)² MgR₂ + MgCl₂ Mg(Cl₂)MgR₂ with R=H and CH₃. In the absence of any solvents, calculations indicate that the formation of the various possible bridged dimers (RMgCl)₂ is substantially exothermic. However, using dimethylether as a model solvent, we show that the formation of the dimer (Me₂O)(CH₃)Mg(Cl₂)Mg(CH₃)(OMe₂) is exothermic only when entropic effects are included.