A stunning example for a spontaneous reaction with a complex mechanism: the vinylidene–acetylene cycloaddition reaction

Kraka, Elfi; Joo, Hyun; Cremer, Dieter

doi:10.1080/00268976.2010.519730

Cited by 21 publications

(24 citation statements)

References 53 publications

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“…3, or Refs. [123][124][125], and in these cases the ability to construct a consistent active space along the entire reaction path, such as afforded by the AVAS procedure, may be valuable.…”

Section: Quantitative Treatment Of Homolytic Bond Dissociation Processesmentioning

confidence: 99%

Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals

Sayfutyarova

Sun

Chan

et al. 2017

J. Chem. Theory Comput.

178

242

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We introduce the atomic valence active space (AVAS), a simple and well-defined automated technique for constructing active orbital spaces for use in multiconfiguration and multireference (MR) electronic structure calculations. Concretely, the technique constructs active molecular orbitals capable of describing all relevant electronic configurations emerging from a targeted set of atomic valence orbitals (e.g., the metal d orbitals in a coordination complex). This is achieved via a linear transformation of the occupied and unoccupied orbital spaces from an easily obtainable single-reference wave function (such as from a Hartree-Fock or Kohn-Sham calculations) based on projectors to targeted atomic valence orbitals. We discuss the premises, theory, and implementation of the idea, and several of its variations are tested. To investigate the performance and accuracy, we calculate the excitation energies for various transition-metal complexes in typical application scenarios. Additionally, we follow the homolytic bond breaking process of a Fenton reaction along its reaction coordinate. While the described AVAS technique is not a universal solution to the active space problem, its premises are fulfilled in many application scenarios of transition-metal chemistry and bond dissociation processes. In these cases the technique makes MR calculations easier to execute, easier to reproduce by any user, and simplifies the determination of the appropriate size of the active space required for accurate results.

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“…3, or Refs. [123][124][125], and in these cases the ability to construct a consistent active space along the entire reaction path, such as afforded by the AVAS procedure, may be valuable.…”

Section: Quantitative Treatment Of Homolytic Bond Dissociation Processesmentioning

confidence: 99%

Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals

Sayfutyarova

Sun

Chan

et al. 2017

J. Chem. Theory Comput.

178

242

View full text Add to dashboard Cite

show abstract

“…For example, in the case of barrier‐less reactions without TS for which an IRC does not exist, a representative path based on Newton trajectories can be used . This led to the surprising result that barrierless reactions such as the chelotropic reaction between methylene and ethene or the spontaneous cycloaddition between vinylidene and acetylene reaction often possess a complex reaction mechanism …”

Section: Unified Reaction Valley Approachmentioning

confidence: 99%

Dieter Cremer's contribution to the field of theoretical chemistry

Kraka

Cremer²

2019

Int J of Quantum Chemistry

Self Cite

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This legacy article reviews the contributions of Dieter Cremer (1944‐2017) to the field of theoretical chemistry, highlighting his major accomplishments in method development and applied quantum chemistry, which has led to many advances in the field. His work reflects an extraordinary breadth and deep understanding of theory, which is needed to solve complex chemical problems. His passion for science has inspired many colleagues in the past and will do so in the future.

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“…Hence, reaction mechanisms can be modelled as minimum energy paths between stable configurations on a 3N-6 multidimensional PES. [31][32][33][34][35]…”

Section: Quantum Mechanics In Chemical Interpretationmentioning

confidence: 99%

Curly arrows, electron flow, and reaction mechanisms from the perspective of the bonding evolution theory

Andrés

González-Navarrete

Safont

et al. 2017

Phys. Chem. Chem. Phys.

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Despite the usefulness of curly arrows in chemistry, their relationship with real electron density flows is still imprecise, and even their direct connection to quantum chemistry is still controversial. The paradigmatic description - from first principles - of the mechanistic aspects of a given chemical process is based mainly on the relative energies and geometrical changes at the stationary points of the potential energy surface along the reaction pathway; however, it is not sufficient to describe chemical systems in terms of bonding aspects. Probing the electron density distribution during a chemical reaction can provide important insights, enabling us to understand and control chemical reactions. This aim has required an extension of the relationships between the concepts of traditional chemistry and those of quantum mechanics. Bonding evolution theory (BET), which combines the topological analysis of the electron localization function (ELF) and Thom's catastrophe theory (CT), provides a powerful method that offers insight into the molecular mechanism of chemical rearrangements. In agreement with the laws of physical and aspects of quantum theory, BET can be considered an appropriate tool to tackle chemical reactivity with a wide range of possible applications. In this work, BET is applied to address a long-standing problem: the ability to monitor the flow of electron density. BET analysis shows a connection between quantum mechanics and bond making/forming processes. Likewise, the present approach retrieves the classical curly arrows used to describe the rearrangements of chemical bonds and provides detailed physical grounds for this type of representation. We demonstrate this procedure using the test set of prototypical examples of thermal ring apertures, and the degenerated Cope rearrangement of semibullvalene.

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A stunning example for a spontaneous reaction with a complex mechanism: the vinylidene–acetylene cycloaddition reaction

Cited by 21 publications

References 53 publications

Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals

Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals

Dieter Cremer's contribution to the field of theoretical chemistry

Curly arrows, electron flow, and reaction mechanisms from the perspective of the bonding evolution theory

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