Table Of ContentHandbook 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.
