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David L Cooper

Publications and source records attributed to David L Cooper.

4 recordsLinked to original sources

Modern valence-bond-like representations of selected D6h "aromatic" rings.

Starting from CASSCF(6,6)/6-31G(d,p) wave functions, we consider different valence-bond (VB)-like interpretations of the pi electron systems for various (constrained) "benzene-like" D(6)(h)() rings, exploiting the invariance of the total wave function to arbitrary nonsingular transformations of the active orbitals. Quantities obtained rather directly from the various calculations provide a fairly consistent ordering of the degree of aromaticity: C(6)H(6) approximately B(6) > N(6) > Al(6) approximately Si(6)H(6) > P(6). Representations based on mutually orthogonal orbitals are found to be somewhat less satisfactory than those that have no such constraints on the overlaps between the active orbitals.

Journal Article↗

Broca's arrow: evolution, prediction, and language in the brain.

Brodmann's areas 44 and 45 in the human brain, also known as Broca's area, have long been associated with language functions, especially in the left hemisphere. However, the precise role Broca's area plays in human language has not been established with certainty. Broca's area has homologs in the great apes and in area F5 in monkeys, which suggests that its original function was not linguistic at all. In fact, great ape and hominid brains show very similar left-over-right asymmetries in Broca's area homologs as well as in other areas, such as homologs to Wernicke's area, that are normally associated with language in modern humans. Moreover, the so-called mirror neurons are located in Broca's area in great apes and area F5 in monkeys, which seem to provide a representation of cause and effect in a primate's environment, particularly its social environment. Humans appear to have these mirror neurons in Broca's area as well. Similarly, genetic evidence related to the FOXP2 gene implicates Broca's area in linguistic function and dysfunction, but the gene itself is a highly conserved developmental gene in vertebrates and is shared with only two or three differences between humans and great apes, five between humans and mice, and eight between humans and songbirds. Taking neurons and portions of the brain as discrete computational segments in the sense of constituting specific Turing machines, this evidence points to a predictive motor and conceptual function for Broca's area in primates, especially for social concepts. In human language, this is consistent with evidence from typological and cognitive linguistics.

Biological Evolution↗

Spin-coupled study of the electronic mechanism of the hetero-Diels-Alder reaction of acrolein and ethene.

Modern valence bond theory, in its spin coupled form, is used to elucidate the electronic rearrangements that take place during the course of the gas-phase hetero-Diels-Alder cycloaddition reaction of s-cis-acrolein (cis-1-oxabutadiene or cis-propeneal) and ethene. It is found that the most dramatic changes to the electronic structure occur in a relatively narrow interval of the reaction pathway soon after the transition state and that the system passes through a geometry at which it can be considered to be significantly aromatic. Although concerted, the reaction is markedly asynchronous, with the breaking of the carbon-oxygen pi bond, and the formation of the new carbon-oxygen sigma bond, "lagging behind" somewhat the other bond-making and bond-breaking processes.

Journal Article↗