Computational Methods in Lanthanide and Actinide Chemistry

Informationen zum Autor Michael Dolg, Institute for Theoretical Chemistry, University of Cologne, Germany. Professor Dolg works in the field of relativistic ab initio pseudopotentials, both their development and their applications. He performed the first wavefunction-based relativistic and correlated ab initio calculations on lanthanide compounds, in 1989, and in 1994 he extended his studies to actinides. He is currently working on various topics in lanthanide and actinide computational chemistry and is one of the leading scientists in this field. Klappentext The f-elements and their compounds often possess an unusually complex electronic structure, governed by the high number of electronic states arising from open f-shells as well as large relativistic and electron correlation effects. A correct theoretical description of these elements poses the highest challenges to theory.Computational Methods in Lanthanide and Actinide Chemistry summarizes state-of-the-art electronic structure methods applicable for quantum chemical calculations of lanthanide and actinide systems and presents a broad overview of their most recent applications to atoms, molecules and solids. The book contains sixteen chapters, written by leading experts in method development as well as in theoretical investigations of f-element systems.Topics covered include: Relativistic configuration interaction calculations for lanthanide and actinide anions Study of actinides by relativistic coupled cluster methods Relativistic all-electron approaches to the study of f- element chemistry Relativistic pseudopotentials and their applications Gaussian basis sets for lanthanide and actinide elements Applied computational actinide chemistryThis book will serve as a comprehensive reference work for quantum chemists and computational chemists, both those already working in, and those planning to enter the field of quantum chemistry for f-elements. Experimentalists will also find important information concerning the capabilities of modern quantum chemical methods to assist in the interpretation or even to predict the outcome of their experiments. Zusammenfassung The f-elements and their compounds often possess an unusually complex electronic structure, governed by the high number of electronic states arising from open f-shells as well as large relativistic and electron correlation effects. A correct theoretical description of these elements poses the highest challenges to theory. Inhaltsverzeichnis Contributors xiiiPreface xvii1 Relativistic Configuration Interaction Calculations for Lanthanide and Actinide Anions 1Donald R. Beck, Steven M. O'Malley and Lin Pan1.1 Introduction 11.2 Bound Rare Earth Anion States 21.3 Lanthanide and Actinide Anion Survey 31.3.1 Prior Results and Motivation for the Survey 31.3.2 Techniques for Basis Set Construction and Analysis 61.3.3 Discussion of Results 91.4 Resonance and Photodetachment Cross Section of Anions 121.4.1 The Configuration Interaction in the Continuum Formalism 131.4.2 Calculation of the Final State Wavefunctions 152 Study of Actinides by Relativistic Coupled Cluster Methods 23Ephraim Eliav and Uzi Kaldor2.1 Introduction 232.2 Methodology 252.2.1 The Relativistic Hamiltonian 252.2.2 Fock-Space Coupled Cluster Approach 252.2.3 The Intermediate Hamiltonian CC method 272.3 Applications to Actinides 302.3.1 Actinium and Its Homologues: Interplay of Relativity and Correlation 312.3.2 Thorium and Eka-thorium: Different Level Structure 352.3.3 Rn-like actinide ions 392.3.4 Electronic Spectrum of Superheavy Elements Nobelium (Z=102) and Lawrencium (Z=103) 422.3.5 The Levels of U4+ and U5+: Dynamic Correlation and Breit Interaction 452.3.6 Relativistic Coupled Cluster Approach to Actinide Molecules 482.4 Summary and Conclusion 493 Relativistic All-Electron Approaches to the Study of f Element Chemistry 55Trond Saue and Luca...

Auteur

Michael Dolg, Institute for Theoretical Chemistry, University of Cologne, Germany. Professor Dolg works in the field of relativistic ab initio pseudopotentials, both their development and their applications. He performed the first wavefunction-based relativistic and correlated ab initio calculations on lanthanide compounds, in 1989, and in 1994 he extended his studies to actinides. He is currently working on various topics in lanthanide and actinide computational chemistry and is one of the leading scientists in this field.

Texte du rabat

The f-elements and their compounds often possess an unusually complex electronic structure, governed by the high number of electronic states arising from open f-shells as well as large relativistic and electron correlation effects. A correct theoretical description of these elements poses the highest challenges to theory. Computational Methods in Lanthanide and Actinide Chemistry summarizes state-of-the-art electronic structure methods applicable for quantum chemical calculations of lanthanide and actinide systems and presents a broad overview of their most recent applications to atoms, molecules and solids. The book contains sixteen chapters, written by leading experts in method development as well as in theoretical investigations of f-element systems. Topics covered include: Relativistic configuration interaction calculations for lanthanide and actinide anions Study of actinides by relativistic coupled cluster methods Relativistic all-electron approaches to the study of f- element chemistry Relativistic pseudopotentials and their applications Gaussian basis sets for lanthanide and actinide elements Applied computational actinide chemistry This book will serve as a comprehensive reference work for quantum chemists and computational chemists, both those already working in, and those planning to enter the field of quantum chemistry for f-elements. Experimentalists will also find important information concerning the capabilities of modern quantum chemical methods to assist in the interpretation or even to predict the outcome of their experiments.

Contenu

Contributors xiii Preface xvii 1 Relativistic Configuration Interaction Calculations for Lanthanide and Actinide Anions 1 Donald R. Beck, Steven M. O'Malley and Lin Pan 1.1 Introduction 1 1.2 Bound Rare Earth Anion States 2 1.3 Lanthanide and Actinide Anion Survey 3 1.3.1 Prior Results and Motivation for the Survey 3 1.3.2 Techniques for Basis Set Construction and Analysis 6 1.3.3 Discussion of Results 9 1.4 Resonance and Photodetachment Cross Section of Anions 12 1.4.1 The Configuration Interaction in the Continuum Formalism 13 1.4.2 Calculation of the Final State Wavefunctions 15 2 Study of Actinides by Relativistic Coupled Cluster Methods 23 Ephraim Eliav and Uzi Kaldor 2.1 Introduction 23 2.2 Methodology 25 2.2.1 The Relativistic Hamiltonian 25 2.2.2 Fock-Space Coupled Cluster Approach 25 2.2.3 The Intermediate Hamiltonian CC method 27 2.3 Applications to Actinides 30 2.3.1 Actinium and Its Homologues: Interplay of Relativity and Correlation 31 2.3.2 Thorium and Eka-thorium: Different Level Structure 35 2.3.3 Rn-like actinide ions 39 2.3.4 Electronic Spectrum of Superheavy Elements Nobelium (Z=102) and Lawrencium (Z=103) 42 2.3.5 The Levels of U4+ and U5+: Dynamic Correlation and Breit Interaction 45 2.3.6 Relativistic Coupled Cluster Approach to Actinide Molecules 48 2.4 Summary and Conclusion 49 3 Relativistic All-Electron Approaches to the Study of f Element Chemistry 55 Trond Saue and Lucas Visscher 3.1 Introduction 55 3.2 Relativistic Hamiltonians 59 3.2.1 General Aspects 59 3.2.2 Four-Component Hamiltonians 61 3.2.3 Two-Component Hamiltonians 65 3.2.4 Numerical Example 69 3.3 Choice of Basis Sets 71 3.4 Electronic Structure Methods 73 3.4.1 Coupled Cluster Approaches 75 3.4.2 Multi-Reference Perturbation Theory 80 3.4.3 (Time-Dependent) Density Functional Theory 82 3.5 Conclusions and Outlook 83 4 Low-Lying Excited States of Lanthanide Diatomics Studied by Four-Component Rela…