Handbook on the Physics and Chemistry of Rare Earths. vol.37 Optical Spectroscopy PDF
Preview Handbook on the Physics and Chemistry of Rare Earths. vol.37 Optical Spectroscopy
Handbook on the Physics and Chemistry of Rare Earths Vol. 37 edited by K.A. Gschneidner, Jr., J.-C.G. Bünzli and V.K. Pecharsky © 2007 Elsevier B.V. All rights reserved. ISSN: 0168-1273/DOI: 10.1016/S0168-1273(07)37036-0 PREFACE Karl A. GSCHNEIDNER Jr., Jean-Claude G. BÜNZLI and Vitalij K. PECHARSKY These elements perplex us in our rearches [sic], baffle us in our speculations, and haunt us in our very dreams. They stretch like an unknown sea before us – mocking, mystifying, and mur- muring strange revelations and possibilities. Sir William Crookes (February 16, 1887) This volume of the Handbook on the Physics and Chemistry of Rare Earth begins with a Dedication to late Professor William (Bill) T. Carnall who pioneered the interpretation of lan- thanide spectra in solutions in the 1960s and 1970s. The Dedication is written by Drs. James V. Beitz and Guokui Liu from Argonne National Laboratory where Bill Carnall spent his entire 37-year scientific career. Optical spectroscopy has been instrumental in the discovery of many lanthanide elements. In return, these elements have always played a prominent role in lighting devices and light conversion technologies (Auer mantles, incandescent lamps, lasers, cathode-ray and plasma displays). They are also presently used in highly sensitive luminescent bio-analyses and cell imaging. This volume is entirely devoted to the photophysical properties of these elements. Its five chapters describe various aspects of lanthanide spectroscopy and its applications. Chapter 231 presents state-of-the-art first-principles f–d calculations of lanthanide energy lev- els and f–d transition intensities. It is followed by a review (chapter 232) on both theoretical and experimental aspects of f–d transitions, a less known field of lanthanide spectroscopy, yet very important for the design of new optical materials. Chapter 233 describes how con- finement effects act on the photophysical properties of lanthanides when they are inserted into nanomaterials, including nanoparticles, nanosheets, nanowires, nanotubes, insulating and semiconductor nanocrystals. The use of lanthanide chelates for biomedical analyses is pre- sented in chapter 234; long lifetimes of the excited states of lanthanide ions allow one to take advantage of time-resolved spectroscopy, which leads to highly sensitive analyses devoid of background effects from the autofluorescence of the samples. The last review (chapter 235) provides a comprehensive survey of near-infrared (NIR) emitting molecular probes and de- vices, from simple chelates to macrocyclic complexes, heterometallic functional edifices, co- ordination polymers and other extended structures. Applications ranging from telecommuni- cations to light-emitting diodes and biomedical analyses are assessed. v vi PREFACE n n−1 Chapter 231. First-principles calculations of 4f → 4f 5d transition spectra by Kazuyoshi Ogasawara, Shinta Watanabe, Hiroaki Toyoshima and Mikhail G. Brik Kwansei Gakuin University, 2-1 Gakuen, Sanda, Japan Due to the growing demand for lasers and phosphors operating in UV and VUV regions, a great deal of attention is being paid now to the thorough analysis of high-lying energy levels n n−1 1 of lanthanide (R) ions arising from their 4f and 4f 5d electronic configurations. This n n−1 1 chapter reviews the recent development of the first-principles analysis of the 4f → 4f 5d spectra of R ions in crystals. It starts with a brief review of the commonly used semi-empirical crystal-field calculations and with a historical overview of the first-principles calculations for multiplet states of metal ions in crystals. A detailed description of the relativistic discrete variational multielectron (DVME) method follows, a first-principles relativistic many-electron calculation method developed by the authors. The major part of the chapter is then devoted to the recent achievements on DVME calculations and analyses of the energy level schemes n n−1 1 and 4f → 4f 5d spectra of R ions in a free state and in crystals. The Dieke diagram is theoretically extended and the origins of peaks in the spectra are clarified based on the explicit many-electron wavefunctions. An application to the analysis of a commercially-used 2+ 2+ blue phosphor, BaMgAl10O17:Eu (BAM:Eu ), is also given. n n−1 Chapter 232. 4f –4f 5d transitions by Gary W. Burdick and Mike F. Reid Andrews University, Berrien Springs, MI, USA and University of Canturbury, Christchurch, New Zealand Numerous applications of lanthanide materials, including scintillators, visible ultraviolet (VUV) lasers, and phosphors for fluorescent lighting and plasma displays, make use of the PREFACE vii n−1 4f 5d excited configuration. Obviously, understanding of these states is crucial to the de- velopment of advanced materials. This chapter reviews an extension of the parametric model n originally developed by Carnall, Wybourne and Dieke to treat 4f spectra. The authors of this chapter show that the extended model may and has been successfully employed to cal- n−1 culate the absorption and emission spectra for the 4f 5d configuration. The review illus- trates how parametrization can be applied to calculate other properties of interest, such as non-radiative relaxation rates, thus explaining the major features of the UV and VUV spec- tra for ions across the entire lanthanide series. The chapter concludes with a discussion of the relationship between parametrized calculations and other approaches, such as ab initio calculations. Chapter 233. Spectroscopic properties of lanthanides in nanomaterials by Guokui Liu and Xueyuan Chen Argonne National Laboratory, USA and Fujian Institute of Research on the Structure of Matter, Fuzhou, China This chapter reviews recent studies on energy levels and excited state dynamics of lan- thanides (R) in nano-structures, which include R-doped dielectric nano-crystals, implanted nano-particles of semiconductors, coated core–shell nano-particles, nano-tubes and nano-balls stuffed with R ions. New phenomena such as the action of confinement on ion–phonon inter- action and its consequences for electronic transitions, energy transfer, and phase transitions are discussed in the light of experimental and theoretical studies reported in the literature. Although the review aims at being comprehensive and covers all the important aspects in the field, emphasis is given to identification and theoretical analysis of various mechanisms for viii PREFACE luminescence enhancement, or quenching, and anomalous size- and temperature-dependence of photophysical properties. Chapter 234. Lanthanide chelates as luminescent labels in biomedical analyses by Takuya Nishioka, Kôichi Fukui, and Kazuko Matsumoto Waseda University and Japan Science and Technology Agency, Tokyo, Japan PREFACE ix Recent advances in time-resolved spectroscopy (TRS) using luminescent lanthanide labels for biomedical analyses are reviewed. The large Stokes shift and long-lived excited states specific to some lanthanide chelates allow the use of TRS for these analyses, which effec- tively removes background fluorescence of the samples. This enables the measurement of very small signals which could not be detected in conventional fluorometric analyses based on organic dye labels. The resulting high signal-to-noise ratios leads to the determination of trace amounts of targeted proteins, nucleic acids or any other biomolecules with unusually high sensitivity. The chapter includes a description of the synthesis of luminescent lanthanide chelates and of their physical properties. The advantage of luminescence resonance energy transfer (LRET) and luminescence quenching are explained in relationship to the specific properties of the lanthanide chelates used as luminescent labels. Medical applications of lan- thanide chelates in immunoassays, DNA hybridization assays, receptor-ligand binding assays, and imaging are reviewed. Chapter 235. Lanthanide near-infrared luminescence in molecular probes and devices by Steve Comby and Jean-Claude G. Bünzli École Polytechnique Fédérale de Lausanne (EPFL), Switzerland Interest for lanthanide-containing near-infrared (NIR) emitting compounds stemmed ini- tially from the development of lasers, optical fibers and amplifiers for telecommunications. Up-conversion processes have also been the subject of much attention. More recently, it was realized that biological tissues are transparent to light in the range 700–1000 nm, allowing optical detection of tumors. This review concentrates mainly on discrete molecular edifices III III III III containing Nd , Er , or Yb , although systems containing other NIR-emitting R ions are also mentioned. It starts with a general description of the photophysical properties of NIR- emitting lanthanide ions and of their sensitization before systematically reviewing the various classes of compounds used for designing NIR-emitting lanthanide probes. Macrocyclic lig- ands are described first (porphyrins, coronands, cryptands, cyclen derivatives, calixarenes), followed by acyclic ligands, among them beta-diketonates are a privileged and much stud- ied group of chelates. New strategies are described, which make use of podands, dendrimers, x PREFACE or self-assembly processes, as well as of sensitization through d-transition metal ions. The overview ends by the description of NIR-emitting ions embedded into extended structures, coordination polymers, inorganic clusters, zeolites, microporous materials, microspheres and nanoparticles. The last part of the chapter focuses on potential applications, including liquid lasers, optical fibers and amplifiers, light-emitting diodes, and analytical applications, includ- ing biomedical analyses. As an aid to future work in the field, comprehensive tables compare III the effectiveness of the chromophores used to date to sensitize the NIR luminescence of Nd , III III Er , and Yb . Handbook on the Physics and Chemistry of Rare Earths Vol. 37 edited by K.A. Gschneidner, Jr., J.-C.G. Bünzli and V.K. Pecharsky © 2007 Elsevier B.V. All rights reserved. ISSN: 0168-1273/DOI: 10.1016/S0168-1273(07)37037-2 ⋆ DEDICATION TOWILLIAM T. CARNALL James V. BEITZ and Guokui LIU Chemistry Division, Argonne National Laboratory, Argonne, IL 60439-4831, USA Contents William T. Carnall (May 23, 1927–June 22, 2003) xiii Appendix xvii Vita xvii Publications xix Journals xix Books and book chapters xxiv Research reports xxvi ⋆ The submitted manuscript has been created by UChicago Argonne, LLC, Operator of Argonne National Labo- ratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up nonex- clusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government. xi xii J.V. BEITZ and G. LIU Dr. William T. Carnall DEDICATION TO WILLIAM T. CARNALL xiii William T. Carnall (May 23, 1927–June 22, 2003) William Thomas Carnall (known to his many friends as Bill) was born in Denver, Colorado on May 23, 1927. He died at age 76 on June 22, 2003 in an automobile accident. Bill graduated from South High School in Denver, Colorado in 1945. He promptly joined the US Navy in which he served briefly as World War II was ending. He earned his B.S. degree in chemistry from Colorado State University in 1950 with highest honors and married Velaine Vanier. They had three children—Richard, Lisa and Bruce. Bill completed his Ph.D. in physical chemistry with a minor in physics at the University of Wisconsin at Madison in 1954 under the direction Prof. John E. Willard. He then began his productive and distinguished 37 year research career at Argonne National Laboratory in Argonne, Illinois. At Argonne National Laboratory, development of nuclear reactors was a significant focus of research from the chartering of the Laboratory in 1946. The light lanthanides in particu- lar were recognized early on to be important fission products due to their many radioactive isotopes and their impact on the neutron economy of nuclear reactors due to those lanthanide isotopes with large neutron absorption cross-sections. In addition, the synthetic actinide ele- ments, an essential component of most nuclear reactors, originally had been expected to ex- hibit lanthanide-like characteristics, including optical spectra, although by the 1950s evidence had accumulated that such was not the case for the most common oxidation states of the light to near mid-series actinide elements. When Bill Carnall joined the Laboratory in 1954 as a chemist in the Chemistry Division, these facts raised a wide variety of issues and opportuni- ties for both fundamental and applied research in areas ranging from separation and removal of lanthanides during reprocessing of spent reactor fuel to development of methods for analy- sis that were rapid and nondestructive. In addition, significant advances in instrumentation, notably the development and commercialization of dual beam recording spectrophotometers that directly measured optical absorbance, were occurring. From a basic science perspective, the parallel development of theories concerning f-electron states and their transitions and the reporting of detailed low temperature spectra of many of the lanthanides in a variety of hosts offered opportunities that Bill seized upon early in his scientific career to increase understanding of the origins of the fingerprint-like character of the optical absorption spectra of trivalent lanthanide ions. He was encouraged to pursue such research by two of the leading figures in heavy element research in the Chemistry Division at Argonne National Laboratory, namely Donald C. Stewart and Paul R. Fields. Stewart had a long standing interest in lanthanide spectroscopy as an analytical tool and Fields was leading an effort to discover new actinide elements using such exotic methods as separation and analy- sis of debris from thermonuclear explosions. A convergence of interests led the U.S. Atomic Energy Commission to fund the building in 1961 of a new hot laboratory research complex in the Chemistry Division that contained not only a suite of chemical laboratories equipped with hoods and gloveboxes designed for radiochemical studies but also a graded series of hot cells 16 that provided the ability to safely handle up to 1 million curies (3.7 × 10 Bq) of 1 MeV gamma emitting isotopes. This new facility provided space for synthesis of novel radioactive compounds and measurement of their properties, including their optical absorption spectra, and was Bill’s research home for most of his scientific career.
The list of books you might like
