Charge sensitivity approach to electronic structure and chemical reactivity / Roman F. Nalewajski, Jacek Korchowiec.

Format:

Book

Author/Creator:

Nalewajski, R. F. (Roman F.)

Contributor:

Korchowiec, Jacek.

Series:

Advanced series in physical chemistry ; v. 8.

Advanced series in physical chemistry ; v. 8

Language:

English

Subjects (All):

Electronic structure.

Reactivity (Chemistry).

Physical Description:

1 online resource (311 p.)

Place of Publication:

Singapore : World Scientific Pub. Co., 1997.

Language Note:

English

Summary:

Charge Sensitivity Analysis (CSA) represents a linear response treatment of molecular systems, based upon the chemical potential and hardness/softness concepts established within density functional theory (DFT). Recently, it has been shown to provide an attractive framework leading to novel approaches to chemical reactivity of open systems. The monograph presents the conceptual and methodological basis of the CSA covering its DFT roots, alternative resolutions and representations, sensitivities of closed and open atomic and molecular systems, charge stability criteria and relaxational effects

Contents:

PREFACE; ADVANCED SERIES IN PHYSICAL CHEMISTRY; INTRODUCTION; CONTENTS; LIST OF ACRONYMS; CHAPTER 1 INTRODUCTORY SURVEY; 1. Global and Regional Equilibria and the Associated Charge Sensitivities; 2. The Chemical Potential/Electronegativity Equalization; 3. Alternative State Variables and Principal Derivatives; 4. Modelling the AIM Hardness Matrix; 5. Direct and Indirect Modelling of Charge Responses; CHAPTER 2 ATOMIC CHARGE SENSITIVITIES; 1. Alternative Representations of Atomic States, Potentials, Derivatives and Their Reduction; 2. Qualitative Discussion of Atomic Sensitivities

3. Reduction of Derivatives: Equipotential Sensitivities4. Diatomic Donor-Acceptor Systems; 4.1. Harpoon Mechanism; 4.2. Interaction Energy; 4.3. Chemical Potential Equalization Perspective on Harpoon Mechanism; 5. Combination Rules; 6. Illustrative Qualitative Applications; 6.1. Electronegativity Equalization Rules; 6.2. Hard-Soft-Acids-and-Bases Principles; 6.3. Directing Influence of Ligands; 7. General Legendre Transformed Representations; 8. More about the Interaction Energy in Donor-Acceptor Systems; CHAPTER 3 CONCEPTS AND RELATIONS OF MOLECULAR CHARGE SENSITIVITY ANALYSIS

1. Hardness and Softness Quantities in the AIM-Resolution2. Charge Sensitivities in the Local Description; 3. Relative Internal Development; 4. Determining Charge Sensitivities from Canonical AIM Hardnesses; 5. In situ Quantities in the Donor-Acceptor Systems; 6. Collective Charge Displacements; 6.1. Populational Normal Modes; 6.2. Minimum Energy Coordinates; 6.3. Collective Modes of Molecular Fragments; CHAPTER 4 CONCEPTS FOR CHEMICAL REACTIVITY; 1. Partitioning of the Fukui Function Indices in Reactive Systems; 2. Internal Hardness Decoupling Modes; 3. Externally Decoupled Modes

4. Inter-Reactant Modes5. Mapping Relations; 6. Stability Considerations; 7. Partitioning of the Interaction Energy; 8. Mutual Polarization of Reactants; 9. Intersecting-State Model of Charge Transfer Processes; CHAPTER 5 ILLUSTRATIVE APPLICATIONS TO MODEL CATALYTIC SYSTEMS; 1. Rutile Surface Clusters and the Water-Rutile System; 1.1. PNM Resolution of the AIM FF Indices; 1.2. Use of the MEC in Diagnosing Surface Clusters; 1.3. Water-Rutile Molecular Chemisorption; 1.4. The Transition-State for the Water Dissociation; 1.5. Polarizational Patterns of the Closed Adsorbate and Substrate

2. Toluene-[V2O5] System2.1. Surface Cluster and Adsorption Arrangements; 2.2. Energetical Considerations; 2.3. Relative Role of the Diagonal and off-Diagonal Isoelectronic Responses; 2.4. Direction of the Inter-Reactant Charge Transfer; 2.5. Relative Role of the P and CT Components in the Overall Isoelectronic Responses; 2.6. Mutual Polarization of Reactants; 2.7. Charge Transfer Induced Displacements; 2.8. Toluene Activation and Surface Reconstruction Trends from the Overall Diagrams; 2.9. External Charge Transfer Effects; 2.10. Concluding Remarks; 3. Allyl - [MoO3] System

3.1. Charge Reconstruction Patterns

Notes:

Description based upon print version of record.

Includes bibliographical references and index.

ISBN:

9789812831002

9812831002