Computational Methods in Lanthanide and Actinide Chemistry E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1115

Veröffentlichungsjahr: 2015

Beschreibung

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.

Leseprobe

Computational Methods in Lanthanide and Actinide Chemistry

Edited by

MICHAEL DOLG

Institute for Theoretical Chemistry,University of Cologne, Germany

This edition first published 2015© 2015 John Wiley & Sons, Inc.

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Library of Congress Cataloging-in-Publication Data

Dolg, Michael, 1958-  pages cm Includes bibliographical references and index.

 ISBN 978-1-118-68831-1 (cloth)1. Rare earth metals. 2. Actinide elements. 3. Chemistry, Inorganic. I. Title. QD172.R2D65 2015 546′.41–dc23

      2014040220

A catalogue record for this book is available from the British Library.

Contributors

Raymond Atta-Fynn, Department of Physics, University of Texas, Arlington, USA

Jochen Autschbach, Department of Chemistry, University at Buffalo, State University of New York, USA

Zoila Barandiarán, Department of Chemistry, Autonomous University of Madrid, Spain.

Enrique R. Batista, Theoretical Division, Los Alamos National Laboratory, USA

Donald R. Beck, Department of Physics, Michigan Technological University, USA

Eric J. Bylaska, Pacific Northwest National Laboratory, USA

Xiaoyan Cao, Theoretical Chemistry, University of Cologne, Germany

Ludovic Castro, Laboratory of Physics and Chemistry of Nano-Objects, National Institute of Applied Sciences, France

Carine Clavaguéra, Laboratoire de chimie moléculaire, Département de chimie, École Polytechnique CNRS, France

Wibe A. de Jong, Lawrence Berkeley National Laboratory, USA

Jean-Pierre Dognon, Laboratoire de Chimie Moléculaire et de Catalyse pour l’énergie, CEA/Saclay, France

Michael Dolg, Institute for Theoretical Chemistry, University of Cologne, Germany

Kenneth G. Dyall, Dirac Solutions, USA

Ephraim Eliav, School of Chemistry, Tel Aviv University, Israel

Niranjan Govind, Pacific Northwest National Laboratory, USA

Uzi Kaldor, School of Chemistry, Tel Aviv University, Israel

Christos E. Kefalidis, Laboratory of Physics and Chemistry of Nano-Objects, National Institute of Applied Sciences, France

Andrew Kerridge, Department of Chemistry, Lancaster University, UK

Laurent Maron, Laboratory of Physics and Chemistry of Nano-Objects, National Institute of Applied Sciences, Toulouse, France

Richard L. Martin, Theoretical Division, Los Alamos National Laboratory, USA

Hiroko Moriyama, Graduate School of Natural Sciences, Nagoya City University, Japan

Steven M. O’Malley, Atmospheric and Environmental Research, USA

Lin Pan, Physics Department, Cedarville University, USA

Lionel Perrin, Laboratory of Physics and Chemistry of Nano-Objects, National Institute of Applied Sciences, France

Kirk A. Peterson, Department of Chemistry, Washington State University, USA

Pekka Pyykkö, Department of Chemistry, University of Helsinki, Finland

Florent Réal, Université Lille CNRS, Laboratoire PhLAM, CNRS UMR 8523, France

Trond Saue, Laboratoire de Chimie et Physique Quantiques, Université Paul Sabatier (Toulouse III), France

Bernd Schimmelpfennig, Institute for Nuclear Waste Disposal (INE), Karlsruhe Institute of Technology (KIT), Germany

Luis Seijo, Department of Chemistry, Autonomous University of Madrid, Spain.

André Severo Pereira Gomes, Université Lille CNRS, Laboratoire PhLAM, CNRS UMR 8523, France

Lidia Smentek, Department of Chemistry, Vanderbilt University, USA

Hiroshi Tatewaki, Graduate School of Natural Sciences, Nagoya City University, Japan

Valérie Vallet, Université Lille CNRS, Laboratoire PhLAM, CNRS UMR 8523, France

Lucas Visscher, Theoretical Chemistry, Amsterdam Center for Multiscale Modeling, VU University Amsterdam, The Netherlands

Ulf Wahlgren, Department of Physics, Stockholm University, AlbaNova University Centre, Sweden

John W. Weare, Department of Chemistry and Biochemistry, University of California San Diego, USA

Anna Weigand, Theoretical Chemistry, University of Cologne, Germany

Florian Weigend, Karlsruhe Institute of Technology, Germany

Ahmed Yahia, Laboratory of Physics and Chemistry of Nano-Objects, National Institute of Applied Sciences, France

Shigeyoshi Yamamoto, School of International Liberal Studies, Chukyo University, Japan

Ping Yang, Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory (PNNL), USA

Preface

Lanthanides and actinides comprise about one-quarter of the known chemical elements collected in the periodic table. Because of their complex electronic structure, the significant electron correlation effects, and the large relativistic contributions, the f-block elements are probably the most challenging group of elements for electronic structure theory. In 1987 Pyykkö reviewed the available relativistic electronic structure calculations for f-element molecules (Inorganica Chimica Acta 139, 243–245,1987). Of the 59 listed studies, 53 dealt with actinides and only 10 with lanthanides. The applied computational methods comprised ab initio Dirac-Hartree-Fock one-center expansion and Dirac-Hartree-Fock-Slater calculations, quasirelativistic all-electron Xα-studies, and semiempirical valence-only approaches like relativistic extended Hückel theory. None of these studies took into account static electron correlation explicitly using a multi-configurational wavefunction or included at an ab initio level the effects of dynamic electron correlation. No applications of modern density functional theory to f-element molecules were reported either. The treatment of relativity included the Dirac one-particle relativity in a few cases explicitly, but mostly in some approximate form, whereas corrections due to the Breit two-particle interaction or arising from quantum electrodynamics were entirely neglected. Relativistic effective core potentials were only available for a few actinides, which certainly also hampered a routine exploration of lanthanide and actinide chemistry with quantum chemical approaches.

Tremendous progress was made in dealing with lanthanide and actinide systems since the 1987 review of Pyykkö appeared, and the field continues to develop quickly. The current book aims to provide the reader an overview of those state-of-the-art electronic structure theory approaches that have been successfully used for f-element systems so far and summarizes examples of their application. The 16 chapters were written by leading experts involved in the development of these methods as well as their application to various aspects of f-element chemistry. From the results of several studies discussed in these contributions it becomes apparent that quantum chemists successfully conquered the field of lanthanide and actinide chemistry and can provide very valuable contributions not merely supplementing experimental studies, but also frequently guiding their setup and explaining their outcome. Moreover, with largely improved theoretical methods and computational resources at hand, it also became possible to obtain new insights with respect to the interpretation of the electronic structure of f-element compounds.

Despite these many encouraging developments, it is appropriate to say that when it comes to lanthanides and actinides modern electronic structure theory currently can accomplish many things, but certainly not all. It is also clear that this book can only provide a snapshot of the current state of affairs. A number of promising computational approaches, e.g., local electron correlation schemes or F12-dependent wavefunctions, are currently developed and already successfully applied to non-f-element systems. They will during the next years most likely significantly extend the array of available methods for quantum chemical studies of lanthanides and actinides. Thus more exciting developments can be anticipated.

Finally I would like to thank all authors of the chapters for their excellent contributions. My thanks also go to the staff at Wiley, i.e., Sarah Higginbotham, Sarah Keegan, and Rebecca Ralf, for their guidance and support during this book project. Last but not least, I’m grateful to Mrs. Peggy Hazelwood for copy-editing and to Mr. Yassar Arafat at SPi for final handling of the proofs.

Michael Dolg

Cologne

May 2014

1Relativistic Configuration Interaction Calculations for Lanthanide and Actinide Anions

Donald R. Beck1,*Steven M. O’Malley2and Lin Pan3

1Department of Physics, Michigan Technological University

2Atmospheric and Environmental Research

3Physics Department, Cedarville University

1.1 Introduction

Lanthanide and actinide atoms and ions are of considerable technological importance. In condensed matter, they may be centers of lasing activity, or act as high temperature superconductors. Because the f-electrons remain quite localized in going from the atomic to the condensed state, a lot of knowledge gained from atoms is transferable to the condensed state. As atoms, they are constituents of high intensity lamps, may provide good candidates for parity non-conservation studies, and provide possible anti-proton laser cooling using bound-to-bound transitions in anions such as La– [1].

In this chapter we will concentrate on our anion work [2–4], which has identified 114 bound states in the lanthanides and 41 bound states in the actinides, over half of which are new predictions. In two anions, Ce– and La–, bound opposite parity states were found, making a total of 3 [Os– was previously known]. Bound-to-bound transitions have been observed in Ce– [5] and may have been observed in La– [6]. We have also worked on many properties of lanthanide and actinide atoms and positive ions. A complete list of publications can be found elsewhere [7].

1.2 Bound Rare Earth Anion States

In 1994, we began our first calculations on the electron affinities of the rare earths [8]. These are the most difficult atoms to treat, due to the open f -subshells, followed by the transition metal atoms with their open d-subshells. At that time, some accelerator mass spectrometry (AMS) measurements of the lanthanides existed [9, 10] which were rough. Larger values might be due to multiple bound states, states were uncharacterized as to dominant configuration, etc.

Local density calculations done in the 1980s had suggested anions were formed by 4f attachments to the incomplete 4f subshell. Pioneering computational work done by Vosko [11] in the early 1990s on the seemingly simple Lu– and La– anions using a combination of Dirac-Fock and local density results suggested instead that the attachment process in forming the anions involved p, not f, electrons.

Our 1994 calculation on a possible Tm anion was consistent with this, in that it showed 4f attachment was not a viable attachment process. Our calculations are done using a Relativistic Configuration Interaction (RCI) methodology [12], which does a Dirac-Hartree-Fock (DHF) calculation [13] for the reference function (s) (dominant configurations). The important correlation configurations (e.g., single and pair valence excitations from the reference configuration[s]) are then added in, using the DHF radials and relativistic screened hydrogenic function (called virtuals), whose effective charge (Z*) is found by minimization of the energy matrix, to which the Breit contributions may be added, if desired.

Experience gained in the mid-1990s suggested that good candidates for bound anion states might be found by combining observed ground and excited state neutral spectra with the computational knowledge that closing an s-subshell might lower the energy ~1.0 eV or adding a 6p-electron to a neutral atom state (7p in the actinides) might lower the energy ~0.25 eV. The variety of energetically low-lying configurations in the observed spectrum of La and Ce suggests a potential for a large number of bound anion states, which has now been computationally confirmed.

As an example of the process, a Tm–4f146s2 anion state might be bound if there were a 4f146s1 state observed in the neutral atom that was less than 1 eV above the ground state. The use of excited states with s/p attachment also has the computationally attractive feature that it avoids, to a good level of approximation, having to compute correlation effects for d and/or f electrons. An s attachment to an excited state can be equivalent to a d attachment to the ground state. The angular momentum expansions for such pair excitations converge slowly, and a lot of energy is associated with (nearly) closed d and/or f subshells. Clearly, it is best to reduce such problems if usable experimental results exist.

It has always been our position to use no more than moderately size d wavefunction expansions. Current limits are about 20,000 symmetry adapted wavefunctions built from fewer than 1 million Slater determinants, and use of two virtuals per l, per shell (n). This allows the “physics” (systematics) to be more visible and reduces the need for “large” computational resources that were frequently unavailable in the “old” days. Development of systematic “rules” is one of the main goals of our research. Some examples follow: (i) determining which correlation effects are most important for a specific property [14, 15], (ii) near conservation of f-value sums for nearly degenerate states [15, 16], (iii) similar conservation of g-value sums [16], (iv) similar conservation of magnetic dipole hyperfine constants [17, 18]. This approach does mean near maximal use of symmetry, creating extra auxiliary computer codes, and increases the necessity of automating data preparation and file manipulation. Much stricter development of this automation is one of the two factors that reduced calculation of the entire actinide row to less than the time it used to take to complete the calculation for one anion (>4 months for Nd–