Optimal control of the initiation of a pericyclic reaction in the electronic ground state#

Bredtmann, Timm; Manz, J.

doi:10.1007/s12039-011-0199-8

Cited by 12 publications

(22 citation statements)

References 81 publications

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“…So, a recent study [172] of the degenerate Cope rearrangement of semibullvalene has shown good agreement with those results where time-dependent quantum simulations have been performed [173,174]. Thus, BET is capable to adequately predict the order, direction, and synchronicity of electron fluxes, providing rather valuable information when studying reaction mechanisms at elementary level.…”

Section: Catastrophetheorysupporting

confidence: 55%

Chemical structure and reactivity by means of quantum chemical topology analysis

Andrés

González-Navarrete

Safont

2015

Computational and Theoretical Chemistry

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Chemical structure and bonding are key features and concepts in chemical systems which are used in deriving structure-property relationships, and hence in predicting physical and chemical properties of compounds. Even though the contemporary high standards in determination, using both theoretical methods and experimental techniques, questions of chemical bonds as well as their evolution along a reaction pathway are still highly controversial. This paper presents a working methodology to determine the structure and chemical reactivity based on the quantum chemical topology analysis.QTAIM and ELF frameworks, based on the topological analysis of the electron density and the electron localization function, respectively, have been used. We have selected two examples studied by the present approach, to show its potential: (i) QTAIM study on the α -Ag 2 WO 4 , for the simulation of Ag nucleation and formation on α -Ag 2 WO 4 provoked in this crystal by the electron-beam irradiation. (ii) An ELF and Thom´s catastrophe theory study for the reaction pathway associated with the decomposition of stable planar hypercoordinate carbon species, CN 3 Mg 3 + .3Chemistry is the science of substances: their structure, their properties, and the reactions that change them into other substances, as Linus These procedures are hugely successful and they can be considered as an energeticsdriven approach to computational theoretical and chemistry. Then, this research field constitutes a central application of quantum chemistry to the study of stationary points of PESs [53] and the pathways connecting them. The shape of an adiabatic PES is conventionally regarded as a function of the nuclear skeleton, ignoring the wealth of information that can be provided by the total electronic charge density distribution ρ(r).The driving force for the nuclear motion is the potential, which arises from In this context, the electronic structure of a molecule is described in real space terms using topological analysis. Beyond the well-known approach of the QTAIM, which relies on the properties of the electron density ρ(r) when atoms interact, topological analysis of different scalar functions can be employed, such as the electron localization function (ELF) method [90][91][92][93]. Originally, ELF can be developed based on the conditional pair density [90] or can be derived from the kinetic energy density [94].In the latter context, ELF is seen as the scaled difference between the positive kinetic energy density and the von Weizsäcker term [95], whereby the scaling function is the 8 kinetic energy density of the homogeneous electron gas (Thomas-Fermi term) [96,97]. The pictures of a molecule as drawn by the QTAIM and ELF analysis are complementary. Thus, the QTAIM analysis is based on the topology of the electron density ρ(r), whereas the ELF analysis is based on the topology of the electron localization function using the conditional probability for the same spin pairs which is closely related to the local excess of kinetic energy due to the Paul...

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Section: Catastrophetheorysupporting

confidence: 55%

Chemical structure and reactivity by means of quantum chemical topology analysis

Andrés

González-Navarrete

Safont

2015

Computational and Theoretical Chemistry

View full text Add to dashboard Cite

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“…[1], and previously in refs. [4,6]. It is easy to predict, however, that the present discovery is not at all restricted to this specific system.…”

Section: Discussionmentioning

confidence: 64%

“…Appendix A This Appendix presents some results of trajectory simulations of the Cope rearrangement of SBV in the electronic ground state, carried out in full dimensionality, which support the simple one-dimensional model which has been adapted from refs. [1,4,6] in order to perform the present quantum dynamics simulations of the pericyclic reaction.…”

Section: Discussionmentioning

confidence: 99%

“…They are superimposed on the horizontal lines for the energies E, and embedded in the potential symmetric double minimum potential energy curve V(x), which is adapted from Refs. [1,4,6]. The reaction times are t r = 21.5 fs and 970 s for E > B and E < B, respectively.…”

Section: Model and Techniquesmentioning

confidence: 99%

“…It has been shown recently that electronic fluxes during pericyclic reactions from reactants (R) to products (P) differ, even qualitatively, for two cases: on one hand with energy E well above the barrier B of the potential energy surface V that separates the domains of R from P (case E > B), and on the other hand with energy E well below B (case E < B), that is, the case of coherent tunneling. [1] Case E > B may be initiated by means of laser pulses, [2][3][4] whereas the other case E < B takes place at rather low temperatures, typically T < 50 K. [5] Specifically, for the model Cope rearrangement of semibullvalene (SBV) with E > B, the electronic fluxes are asynchronousthe electrons flow out of an "old" bond which is broken in R, before they flow into the "new" bond which is formed in P. In contrast, for E < B, all electronic fluxes are synchronous. [1] The different results for the electronic fluxes serve as motivation for the present search for discrepancies between the nuclear flux densities for the two cases, E > B versus E < B.…”

Section: Introductionmentioning

confidence: 99%

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