Soma Duley

Update 2 of: Electrophilicity Index.

6.1. Molecular Vibrations PR58 6.2. Molecular Internal Rotations PR58 6.3. Chemical Reactions PR58 7. Dynamical Variants PR62 7.1. Quantum Fluid Density Functional Theory PR62 7.2. Atom-Field Interactions PR62 7.3. Ion-Atom Collisions PR62 7.4. Chemical Kinetics PR62 8. Spin Dependent Generalizations PR63 8.1. {N, Ns, v(r b)} Representation PR63 8.2. {NR, N , v(r b)} Representation PR64 9. Conclusions PR65 10. Abbreviations and Symbols of Some Important Subjects/Quantities PR

Understanding local electrophilicity/nucleophilicity activation through a single reactivity difference index

A local reactivity difference index R(k) is shown to be able to predict the local electrophilic and/or nucleophilic activation within an organic molecule. Together with the electrophilic and/or nucleophilic behavior of the center k given by the sign, the magnitude of the R(k) index accounts for the extent of the electronic activation, a behavior that allows for the use of the R(k) index as a measure of the molecular reactivity especially in polar processes.

Bonding, aromaticity, and structure of trigonal dianion metal clusters.

Various isomers of the trigonal dianion metal clusters, X  32− , X = Be, Mg, Ca, and their mono‐ and disodium complexes are optimized at the B3LYP/6‐311+G(d) level. Different conceptual density functional theory based reactivity descriptors as well as the induced magnetic field values are calculated to understand the stability and aromaticity of these systems. Possibility of bond stretch isomerism is explored. Genetic algorithm results lend additional insights into the structures of these isomers.

Aromaticity in all-metal annular systems: the counter-ion effect

The effect of counterions on the bonding, stability and aromaticity of trigonal dianion metal clusters has been analyzed through the behavior of various conceptual density functional theory based reactivity descriptors and the nucleus independent chemical shift calculated at different levels of theory, comprising one-determinant approaches and beyond (QCISD, CASSCF(8,8) and NEVPT2), for a proper benchmarking. Although several important insights into the counter-ion effects are obtained, much needs to be done in order to have a transparent idea therein.

Structure-stability diagrams and stability-reactivity landscapes: a conceptual DFT study

Electrophilicity and hardness have been shown to be adequate in constructing structure-stability diagrams. Maximum hardness principle and minimum electrophilicity principle provide a rough guide toward locating the domains of stability and reactivity in a fitness landscape. Bonding in solids, aromaticity, magic alkali clusters, bond—stretch isomers, multivalent superatoms, etc. have been analyzed within this purview.

A conceptual density functional study of structure, bonding, reactivity and the possibility of bond-stretch isomerism in some neutral sulfur clusters, S n (n=3-8)

Geometries of different isomers of various neutral sulfur clusters, S n (n=3–8) are optimized at the B3LYP/6-311+G* level of theory. Their stability and aromaticity behavior are analyzed in terms of the conceptual density functional theory-based reactivity descriptors and the associated electronic structure principles. The nucleus-independent chemical shift lends additional support. Possibility of bond-stretch isomerism in these clusters is explored.

Some novel molecular frameworks involving representative elements

Several new molecular frameworks with interesting structures, based on clusters of main group elements have been studied at different levels of theory with various basis sets. Conceptual density functional theory based reactivity descriptors and nucleus independent chemical shift provide important insights into their bonding, reactivity, stability and aromaticity.

Heterotrimetallic compounds containing Mo–M–Li [M = K, Rb and Cs] clusters: synthesis, structure, bonding, aromaticity and theoretical investigations of Li2M2 [M = K and Rb] and Cs4 rings

A new polydentate fac-trioxo molybdenum complex, [MoO(3)L](3-) {LH(3) = nitrilotriacetic acid}, has been synthesized by the reaction of lithium molybdate with iminodiacetic acid. The trinegative complex anion coordinates the alkali metal cations, K(+), Rb(+) or Cs(+). The potassium, rubidium and cesium complexes, [Li{K(H(2)O)(2)}MoO(3)L](n) (1), [Li{Rb(H(2)O)(2)}MoO(3)L](n) (2) and [Cs{Li(H(2)O)}(2)MoO(3)L](n) (3), form heterotrimetallic coordination chains, containing planar rings of Li(2)M(2) (M = K or Rb) and Cs(4). Theoretical investigations on these rings were carried out using NICS calculations and ab initio ring current maps, revealing aromaticity to be of limited significance.

Aromaticity and conceptual density functional theory

Aromaticity is one of the most fascinating popular qualitative chemical concepts in chemistry1–4. Michael Faraday5 isolated benzene by distillation in 1825. He noticed that although benzene is an unsaturated compound with H : C :: 1 : 1 it is much less reactive than the related unsaturated aliphatic...