Aromaticity
Modern Computational Methods and Applications
- 1st Edition - May 14, 2021
- Editor: Israel Fernandez
- Language: English
- Paperback ISBN:9 7 8 - 0 - 1 2 - 8 2 2 7 2 3 - 7
- eBook ISBN:9 7 8 - 0 - 1 2 - 8 2 2 7 4 3 - 5
Evaluating the aromaticity of a molecular system and the influence of this concept on its properties is a crucial step in the development of novel aromatic systems. Modern co… Read more
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Request a sales quoteEvaluating the aromaticity of a molecular system and the influence of this concept on its properties is a crucial step in the development of novel aromatic systems. Modern computational methods can provide researchers with a high level of insight into such aromaticity, but identifying the most appropriate method for assessing a specific system can prove difficult. Aromaticity: Modern Computational Methods and Applications reviews the latest state-of-the-art computational methods in this field and discusses their applicability for evaluating the aromaticity of a system.
In addition to covering aromaticity for typical organic molecules, this volume also explores systems possessing transition metals in their structures, macrocycles and even transition structures. The influence of the aromaticity on the properties of these species (including the structure, magnetic properties and reactivity) is highlighted, along with potential applications in fields including materials science and medicinal chemistry. Finally, the controversial and fuzzy nature of aromaticity as a concept is discussed, providing the basis for an updated and more comprehensive definition of this concept.
Drawing on the knowledge of an international team of experts, Aromaticity: Modern Computational Methods and Applications is a unique guide for anyone researching, studying or applying principles of aromaticity in their work, from computational and organic chemists to pharmaceutical and materials scientists.
- Reviews a range of computational methods to assess the aromatic nature of different compounds, helping readers select the most useful tool for the system they are studying
- Presents a complete guide to the key concepts and fundamental principles of aromaticity
- Provides guidance on identifying which variables should be modified to tune the properties of an aromatic system for different potential applications
Computational and organic chemists, researchers interested in aromaticity, experimental chemists working on aromatic compounds, and materials scientists
- Cover Image
- Title Page
- Copyright
- Table of Contents
- Contributors
- Forword
- 1 Aromaticity in molecules and transition structures: from atomic and molecular orbitals to simple ring current models
- Abstract
- Introduction
- Aromaticity in Hückel and Heilbronner–Möbius theories
- Aromaticity in SCF-MO and DFT theories
- Aromaticity and valence bond theory
- Ring currents and atomic orbitals in aromatic systems
- Summary
- Acknowledgements
- References
- 2 Overview of the computational methods to assess aromaticity
- Abstract
- Introduction
- Molecular orbital-based methods
- Adaptive Natural Density Partitioning
- Energy-based methods
- Aromatic stabilization energy
- Isomerization stabilization energy
- Harmonic oscillator stabilization energy
- Magnetic-based methods
- Magnetic susceptibility anisotropy
- Diamagnetic susceptibility exaltation
- 1H-NMR chemical shifts
- Nucleus-independent chemical shift
- Multidimensional NICS
- Anisotropy of the induced current density
- Vorticity of the current density tensor
- Geometry-based methods
- Harmonic oscillator model of aromaticity
- Bird index
- Electron delocalization methods
- Electron localization function
- Para-delocalization index
- Fluctuation index
- Electron density-based methods
- Ellipticity index
- Conclusions
- References
- 3 Molecular geometry as a source of electronic structure of π-electron systems and their physicochemical properties: Molecular geometry as a source of electronic structure of π-electron systems
- Abstract
- Introduction
- Bond length and its multiplicity
- Geometry-based indices of aromaticity
- Applications
- Summary
- References
- 4 NICS—Nucleus-independent Chemical Shift
- Historical and physical background of NICS
- Evolution of NICS as an aromaticity index
- The importance of dissected NICS
- NICS beyond π-systems
- How NICS compares to other indices
- NICS in practice
- References
- 5 Current density, current-density pathways, and molecular aromaticity
- Abstract
- Magnetic fields in quantum mechanics
- Current density
- Current-density susceptibility
- Current-density vector field
- Nuclear magnetic shielding
- Nuclear magnetic shieldings and current densities
- Magnetic susceptibilities and closed-shell paramagnetic molecules
- Treatment of the gauge origin in quantum chemistry
- The gauge-including magnetically induced current method
- Investigating current-density pathways in molecules
- Integrating the strength of the current density
- The aromatic ring-current criterion
- Aromatic pathways in polycyclic molecules
- Aromatic and antiaromatic porphyrinoids
- Möbius-twisted molecules
- Carbon nanostructures
- Aluminum clusters
- Scope and limitations of the GIMIC method
- References
- 6 Quantifying aromaticity according to the energetic criterion
- Abstract
- Introduction
- Resonance energy
- Aromatic stabilization energies
- The isomerization stabilization energy method
- Aromatic stabilization energies from the block-localized wave function method
- Aromatic stabilization energies derived from energy decomposition analysis
- Quantification of aromaticity in expanded porphyrins
- Relationship between energetic indices and nonenergetic descriptors for aromaticity
- Summary
- Acknowledgments
- References
- 7 Aromaticity descriptors based on electron delocalization
- Abstract
- Introduction
- Methodology
- Aromaticity indices
- Computational details
- Discussion
- Conclusions
- Acknowledgments
- References
- 8 The electron density of delocalized bonds (EDDBs) as a measure of local and global aromaticity
- Abstract
- Introduction
- Electron density of delocalized bonds
- The RunEDDB program
- EDDBP as a local aromaticity descriptor
- Visualization of global aromaticity using the EDDBG/H(r) function
- Summary
- Acknowledgments
- References
- 9 Conceptual density functional theory and aromaticity
- Abstract
- Introduction
- Conceptual density functional theory
- Aromaticity and antiaromaticity
- Conclusions
- Acknowledgments
- References
- 10 Antiaromatic compounds: a brief history, applications, and the many ways they escape antiaromaticity: Antiaromatic compounds
- Abstract
- Introduction
- Why can't we make cyclobutadiene?
- References
- 11 Cycloaromatization reactions
- Abstract
- Introduction—cycloaromatization reactions: making radicals without using radicals
- Unusual electronic features of cycloaromatization reactions
- Molecular orbital analysis of cycloaromatization reactions
- Ionic and zwitterionic cycloaromatizations
- Metal-catalyzed cycloaromatizations
- Five-membered heterocyclic diradicals
- Secondary aromaticity effects in cycloaromatization processes
- Conclusions
- Acknowledgment
- References
- 12 Baird aromaticity in excited states and open-shell ground states
- Abstract
- Introduction
- Theoretical derivation of Baird's rule
- Assessing excited-state aromaticity computationally
- Multidimensional character of aromaticity
- Illustrative applications
- Concluding remarks and open challenges
- References
- 13 Global aromaticity in 2D macrocyclic polyradicaloids and 3D fully conjugated molecular cages
- Abstract
- Introduction
- Macrocyclic polyradicaloids with global aromaticity
- Global antiaromaticity in transition state
- 3D global aromaticity in fully conjugated diradicaloid cages
- Conclusion and outlook
- Acknowledgments
- References
- 14 Spherical aromaticity in inorganic chemistry
- Abstract
- Introduction
- Systems with S-supershell filled
- Systems with P-supershell filled
- Conclusions
- Acknowledgments
- References
- Index
- No. of pages: 516
- Language: English
- Edition: 1
- Published: May 14, 2021
- Imprint: Elsevier
- Paperback ISBN: 9780128227237
- eBook ISBN: 9780128227435
IF
Israel Fernandez
Dr. Israel Fernandez (Madrid, 1977) studied Chemistry at the Universidad Complutense de Madrid (UCM). After obtaining his PhD degree (with honors) under the supervision of Prof. M. A. Sierra, he joined the Theoretical and Computational Chemistry group of Prof. G. Frenking at the Philipps-Universität Marburg as a postdoctoral researcher. He received several awards including the Julián Sanz del Río award and the Barluenga's medal. At present, he is Profesor Titular at the UCM. His current research is focused on both the bonding situation of organic and organometallic compounds and their reactivity.
Affiliations and expertise
Department of Organic Chemistry, Complutense University of Madrid, Madrid, SpainRead Aromaticity on ScienceDirect