Conceptual Density-Functional Theory for General Chemical Reactions, Including Those That Are Neither Charge- nor Frontier-Orbital-Controlled. 2. Application to Molecules Where Frontier Molecular Orbital Theory Fails

2007 ◽  
Vol 3 (2) ◽  
pp. 375-389 ◽  
Author(s):  
James S. M. Anderson ◽  
Junia Melin ◽  
Paul W. Ayers
Keyword(s):  
Density Functional Theory ◽  
Chemical Reactions ◽  
Density Functional ◽  
Frontier Molecular Orbital ◽  
Molecular Orbital Theory ◽  
Frontier Orbital ◽  
Orbital Theory ◽  
Conceptual Density Functional Theory ◽  
Functional Theory ◽  
General Chemical

The ozonolysis of ortho-xylene and its relevance to the history of the benzene problem

2001 ◽  
Vol 79 (8) ◽  
pp. 1278-1283 ◽  
Author(s):  
Saul Wolfe ◽  
Zheng Shi
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Transition States ◽  
Historical Analysis ◽  
Valence Bond ◽  
Basis Set ◽  
Frontier Molecular Orbital ◽  
Initial Attack ◽  
Orbital Theory ◽  
Functional Theory

Using B3LYP density functional theory in conjunction with the 6-311++G** basis set, the relative rates of the initial rate-determining attack of ozone upon the carbon—carbon bonds of o-xylene are found to be 4,5- [Formula: see text] 3,4- > 2,3- > 1,2-. With the assumption that the final products glyoxal (G), methylglyoxal (M), and dimethylglyoxal (D) are determined by the site of the initial attack, and taking statistical factors into account, the ratio G:M:D is calculated to be 3:2:1. This is close to the value found experimentally, and identical to the result predicted by the contention that two nearly equivalent Kekulé–Pauling valence bond (resonance) structures of o-xylene exist and each localized carbon—carbon double bond of these structures is oxidized at the same rate. Although Frontier Molecular Orbital theory also predicts a 3:2:1 ratio of G:M:D, this theory incorrectly predicts that the initial attack of ozone will take place at the 1,2- and 4,5- bonds, with 1,2-attack slightly preferred. These results are discussed in relation to a recent historical analysis of the benzene problem, and it is concluded that since the products of ozonolysis of o-xylene are determined by the relative energies of the transition states leading to the four possible primary ozonides, these transition states should be the focus of theory.Key words: Kekulé structure, resonance, frontier orbital theory, density functional theory, kinetics.

scholarly journals Explicit Polarization (X-Pol) Potential Using ab Initio Molecular Orbital Theory and Density Functional Theory†

2009 ◽  
Vol 113 (43) ◽  
pp. 11656-11664 ◽  
Author(s):  
Lingchun Song ◽  
Jaebeom Han ◽  
Yen-lin Lin ◽  
Wangshen Xie ◽  
Jiali Gao
Keyword(s):  
Density Functional Theory ◽  
Ab Initio ◽  
Molecular Orbital ◽  
Density Functional ◽  
Molecular Orbital Theory ◽  
Orbital Theory ◽  
Functional Theory

scholarly journals Computational Study of the Structure of a Sepiolite/Thioindigo Mayan Pigment

2012 ◽  
Vol 2012 ◽  
pp. 1-6 ◽  
Author(s):  
Manuel Alvarado ◽  
Russell C. Chianelli ◽  
Roy M. Arrowood
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Color Change ◽  
Computational Study ◽  
Experimental Studies ◽  
Computational Studies ◽  
Molecular Orbital Theory ◽  
Orbital Theory ◽  
Functional Theory ◽  
Best Fit

The interaction of thioindigo and the phyllosilicate clay sepiolite is investigated using density functional theory (DFT) and molecular orbital theory (MO). The best fit to experimental UV/Vis spectra occurs when a single thioindigo molecule attaches via Van der Waals forces to a tetrahedrally coordinated cation with an additional nearby tetrahedrally coordinated also present. The thioindigo molecule distorts from its planar structure, a behavior consistent with a color change. Due to the weak interaction between thioindigo and sepiolite we conclude that the thioindigo molecule must be trapped in a channel, an observation consistent with previous experimental studies. Future computational studies will look at the interaction of indigo with sepiolite.

Fractional electron number, temperature, and perturbations in chemical reactions

2016 ◽  
Vol 18 (22) ◽  
pp. 15070-15080 ◽  
Author(s):  
Ramón Alain Miranda-Quintana ◽  
Paul W. Ayers
Keyword(s):  
Density Functional Theory ◽  
Chemical Reactions ◽  
Density Functional ◽  
Mathematical Framework ◽  
Electron Number ◽  
Conceptual Density Functional Theory ◽  
Functional Theory

The mathematical framework of conceptual density functional theory is extended to use the eigenstates and eigenvalues of perturbed subsystems. This unites, justifies, and extends, several previously proposed models.

Radiation Tolerance of A2Ti2O7 Materials - A Question of Bonding?

2006 ◽  
Vol 985 ◽  
Author(s):  
Karl Whittle ◽  
Gregory R Lumpkin ◽  
Katherine L Smith ◽  
Mark G Blackford ◽  
Elizabeth J Harvey ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Band Structure ◽  
Nuclear Waste ◽  
Density Functional ◽  
Radiation Stability ◽  
Radiation Tolerance ◽  
Molecular Orbital Theory ◽  
New Materials ◽  
Orbital Theory ◽  
Functional Theory

AbstractThe resistance of Ln2Ti2O7 (Ln=lanthanide) compounds to radiation damage is an important topic in the understanding and development of new materials by which radioactive nuclear waste can safely be immobilised. A model has been developed, from previously published density functional theory and molecular orbital theory simulations of the band structure for Ln2Ti2O7 materials. This model provides a chemical interpretation of radiation stability.

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