DV-X@a for Advanced NANO materials and other Interesting Topics in Materials Science

467 Pages·2003·28.141 MB·English

by  Erkki J. Brandas, Hiorohiko Adachi, Masayuki Uda, Rika Sekine (Eds.)

EDITORIAL BOARD
Jiri Cizek (Waterloo, Canada)
David P Craig (Canberra, Australia)
Raymond Daudel (Paris, France)
Ernest R. Davidson (Bloomington, Indiana)
George G. Hall (Nottingham, England)
Jan Linderberg (Aarhus, Denmark)
Fredrick A. Matsen (Austin, Texas)
Roy McWeeny (Pisa, Italy)
William H. Miller (Berkley, California)
Keiji Morokuma (Atlanta, Georgia)
Josef Paldus (Waterloo, Canada)
Ruben Pauncz (Haifa, Israel)
Siegrid Peyerimhoff (Bonn, West Germany)
John A. Pople (Evanston, Illinois)
Alberte Pullman (Paris, France)
Pekka Pyykkij (Helsinki, Finland)
Leo Radom (Canberra, Australia)
Klaus Ruedenberg (Ames, Iowa)
Henry F. Schaefer III (Athens, Georgia)
Isaiah Shavitt (Columbus, Ohio)
Per Siegbahn (Stockholm, Sweden)
Au-Chin Tang (Changchun, People’s Republic of China)
Rudolf Zahradnik (Prague, Czech Republic)
ADVISORY EDITORIAL BOARD
David M. Bishop (Ottawa, Canada)
Giuseppe Del Re (Naples, Italy)
Fritz Grein (Fredericton, Canada)
Mu-Sik Jhon (Seoul, Korea)
Mel Levy (New Orleans, Louisiana)
Jens Oddershede (Odense, Denmark)
Mark Ratner (Evanston, Illinois)
Dermis Salahub (Quebec, Canada)
Hare1 Weinstein (New York, New York)
Robert E. Wyatt (Austin, Texas)
Tokio Yamabe (Kyoto, Japan)
ADVANCES IN
QUANTUM CHEMISTRY
DV-Xa FOR ADVANCED NAN0 MATERIALS AND OTHER
INTERESTING TOPICS IN MATERIALS SCIENCE
EDITORS
JOHN R. SABIN ERKKI BtiNDAS
QUANTUM THEORY PROJECT DEPARTMENT OF QUANTUM CHEMISTRY
UNIVERSITY OF FLOP.IDA UPPSALA UNIVERSITY
GAINESVILLE, FLORIDA UPPSALA, SWEDEN
FOUNDING EDITOR
PER-OLOV LiiWDINt
GUEST EDITORS
ERKKI J. BtiNDAS HIOROHIKO ADACHI
DEPARTMENT OF QUANTUM CHEMISTRY KYOTO UNIVERSITY
UPPSALA UNIVERSITY DEPARTMENT OF MATERIALS
UPPSALA, SWEDEN SCIENCE AND ENGINEERLNG
KYOTO. JAPAN
MASAYUKI UDA RIKA SEKINE
WASEDA UNIVERSITY DEPARTMENT OF CHEMISTRY
DEPARTMENT OF MATERIALS SHIZUOKA UNIVERSITY
SCIENCE AND ENGINEERING SHIZUOKA, JAPAN
TOKYO, JAPAN
VOLUME 42
AP
0
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Contributors
Ntunbers in parentheses indicate the pages on which the authors' contributions begin.
Hirohiko Adachi ,1( ,76 145, 175), Department of Materials Science and Engineering,
Kyoto University, Sakyo, Kyoto 606-8501, Japan
Matti Alatalo (127), Laboratory of Physics, Helsinki University of Technology, .P .O
Box 1100, 02015 HUT, Finland
Hideki Araki (109), Department of Materials Science and Engineering, Osaka
University, 1-2 Yamada-oka, Suita, Osaka, 565-0871, Japan
Erkki J. Briindas (383), Department of Quantum Chemistry, Uppsala University, Box
518, S-751 20 Uppsala, Sweden
Mads Brandbyge (299), Mikroelektronik Centret (MIC), Technical University of
Denmark, Bldg. 345E, DK-2800 Lyngby, Denmark
Hyunju Chang (163), Advanced Materials Division, Korea Research Institute of
Chemical Technology, Taejon, 305-600, Korea
Yonngmin Choi (163), Advanced Materials Division, Korea Research Institute of
Chemical Technology, Taejon, 305-600, Korea
Don Ellis (35), Department of Physics & Astronomy and Institute of Environmental
Catalysis, Northwestern University, Evanston IL 60208
Noboru Esashi (439), School of Science, Kwansei Gakuin University 1-2 Gakuen,
,S anda, Hyogo 669-1337, Japan
Kiiniehika Fukushima (223), Advanced Energy System Design and Engineering
Department, Isogo Engineering Center, Toshiba Corporation, ,8 Shinsugita-cho,
Isogo-ku, Yokohama, 235-8523, Japan
Talsuya Hagiwara (187), Department of Environmental Chemistry and Materials,
Okayama University, 3-1-1 Tsushima-Naka, Okayama 700-8530, Japan
Yoshinori Hayafuji (239, 439), School of Science, Kwansei Gakuin University 1-2
Gakuen, Sanda, Hyogo 669-1337, Japan
M. Hoshino (399), The Institute of Physical and Chemical Research 2-1, Hirosawa,
Wako, Saitama 351-0198, Japan
E. Iguehi (215), Division of Materials Science and Engineering, Graduate School of
Engineering, Yokohama National University, Tokiwadai, Hodogaya-ku, Yokohama
,1058-04,'7 Japan
iiix
vix SROTUBIRTNOC
Takugo Ishii (67), Department of Materials Science and Engineering, Osaka
University, 1-2 Yamada-oka, Suita, Osaka, 565-0871, Japan
Takamasa Isobe (465), Department of Materials Science, Shonan Institue of
Technology, 1-1-25 Tsujido-nishikaigan, Fujisawa, 251-8511 Japan
Shigeyuki Ito (263), Department ofrMaterials Science and Engineering, Graduate
School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-
8603, Japan
Shiniehi Itoh (209), Kyoto University of Education, Fukakusa Fujimori-cho ,1
Fushimi, Kyoto, 612-8522, Japan
Tomnko Jimbo (453), Hitachi, Ltd., Device Development Center, 16-3, Shinmachi
6-chome, Ome-shi, Tokyo 198-8512, Japan
Lfiszl6 Kiiv6r (331), Institute of Nuclear Research of the Hungarian Academy of
Sciences .OR Box ,15 H-4001 Debrecen, Hungary
Yukinori Koyama (145), Department of Materials Science and Engineering, Kyoto
University, Sakyo, Kyoto 606-8501, Japan
J. Kuriplaeh (77), Department of Low Temperature Physics, Charles University,
V Holegovi6kfich ,2 CZ-180 00 Prague ,8 Czech Republic
Jae Do Lee (163), Advanced Materials Division, Korea Research Institute of Chemical
Technology, Taejon, 305-600, Korea
Yi Liu (315), Department of Materials Science and Engineering, Graduate School of
Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
Hiroshi Maeda (275), Department of Manufacturing Science, Osaka University, 2-1,
Yamada-oka, Suita, Osaka 565-0871, Japan
Shui Matsuo (407), Department of Chemistry, Faculty of Science, Fukuoka
University, Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan
Fumiyoshi Minami (275), Department of Manufacturing Science, Osaka University,
2-1, Yamada-oka, Suita, Osaka 565-0871, Japan
Yoshinari Miura (187), Department of Environmental Chemistry and Materials,
Okayama University, 3-1-1 Tsushima-Naka, Okayama 700-8530, Japan
Masataka Mizuno (109), Department of Materials Science and Engineering, Osaka
University, 1-2 Yamada-oka, Suita, Osaka, 565-0871, Japan
Masahiko Morinaga (263,315), Department of Materials Science and Engineering,
Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya
464-8603, Japan
Jos6 Luis Mozos (299), Instituto de Ciencia de Materiales de Barcelona - CSIC,
08193 Bellaterra, Barcelona, Spain
Takeshi Mukoyama (283), Kansai Gaidai University, Hirakata, Osaka, 573-1001
Japan
Yasuji Muramatsu (353), Kansai Research Establishment, Japan Atomic Energy
Research Institute (JAERI) Kouto, Mikazuki, Sayo-gun, Hyogo 679-5148, Japan
SROTUBIRTNOC xv
~,gnes Nagy (363), Department of Theoretical Physics, University of Debrecen,
0104I-I Debrecen, Hungary
Yoshiyuki Nakajiina (399, 419), Riken Keiki Co. Ltd., Research Department 2-7-6,
Azusawa, Itabashi-ku, Tokyo 174-8744, Japan
ttirohide Nakamatsu (419), Institute for Chemical Research, Kyoto University,
Gokasho, Uji, Kyoto 611-0011, Japan
ttiroshi Nakatsugawa (215), Division of Materials Science and Engineering,
Graduate School of Engineering, Yokohama National University, Tokiwadai,
Hodogaya-ku, Yokohama 240-8501, Japan
Tokuro Nanba (187), Department of Environmental Chemistry and Materials,
Okayama University, 3-1-1 Tsushima-Naka, Okayama 700-8530, Japan
Fumiyasu Oba (175), Department of Materials Science and Engineering, Case
Western Reserve University, 203 White Bldg., 10900 Euclid Avenue, Cleveland,
Ohio 44106-7204, USA (from September 2002)
Kazuyoshi Ogasawara ,1( 67), Department of Materials Science and Engineering,
Kyoto University, Sakyo, Kyoto 606-8501, Japan
Yasuhiko Ohama (439), Neutron Scattering Laboratory, Institute for Solid State
F'hysics, University of Tokyo, Shirakata 106-1, Tokai 319-1106, Japan
Yasnaki Oohara (215), Neutron Scattering Laboratory, Institute for Solid State
Physics, University of Tokyo, Shirakata 106-1, Tokai 319-1106, Japan
Pablo Ordejrn (299), Instituto de Ciencia de Matariales de Barcelona - CSIC, 08193
Bellaterra, Barcelona, Spain
M.d. Puska (127), Laboratory of Physics, Helsinki University of Technology, .P .O
Box 1100, 02015 HUT, Finland
Yoshiyuki Sakai (429), Department of Industrial Education, Ashiya University, 13-22,
Rokurokuso-cho, Ashiya, Hyogo, Japan
Taketo Sakuma (23), Department of Advanced Materials Science, Graduate School
e,f Frontier Science, The University of Tokyo 7-3-1 Hongo, Bunkyo-ku, Tokyo
,6568-311 Japan
Masayoshi Seike (239), School of Science, Kwansei Gakuin University 1-2 Gakuen,
,S anda, Hyogo 669-1337, Japan
Yasuharu Shirai (109), Department of Materials Science and Engineering, Osaka
University, 1-2 Yamada-oka, Suita, Osaka, 565-0871, Japan
Kaori Shirozu (407), Department of Chemistry, Faculty of Science, Fukuoka
University, Nanakuma, Jonan-ku, akourkuF 814-0180, Japan
Mojimir gob (77), Institute of Physics of Materials, Academy of Sciences of the
Czech Republic, Zi~kova ,22 CZ-616 26 Brno, Czech Republic
It. Sormann (77), Institut ftir Theoretische Physik, Technische Universit/it Graz,
Petersgasse ,61 A-8010 Graz, Austria
Knrt Stokbro (299), Mikroelektronik Centret (MIC), Technical University of
Denmark, Bldg. 345E, DK-2800 Lyngby, Denmark
ivx SROTUBIRTNOC
Sunao Sugihara (465), Department of Materials Science, Shonan Institue of
Technology, 1-1-25 Tsujido-nishikaigan, Fujisawa, 251-8511 Japan
Wataru Takahara (275), Department of Manufacturing Science, Osaka University,
2-1, Yamada-oka, Suita, Osaka 565-0871, Japan
Ken-lehi Takai (239), School of Science, Kwansei Gakuin University 1-2 Gakuen,
Sanda, Hyogo 669-1337, Japan
Isao Tanaka (145, 175), Department of Materials Science and Engineering, Kyoto
University, Sakyo, Kyoto 606-8501, Japan
K. Tanaka (239), School of Science, Kwansei Gakuin University 1-2 Gakuen, Sanda,
Hyogo 669-1337, napaJ
Yuiehi Tateishi (407), Department of Chemistry, Faculty of Science, Fukuoka
University, Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan
Jeremy Taylor (299), Mikroelektronik Centret (MIC), Technical University of
Denmark, Bldg. 345E, DK-2800 Lyngby, Denmark
Yoko Uehida (453), Hitachi, Ltd., Semiconductor & Integrated Circuits, 16-3,
Shinmachi 6-chome, Ome-shi, Tokyo 198-8512, Japan
Masayuki Uda (283, 399, 419, 453), Department of Materials Science and
Engineering, Waseda University, Shinjuku, Tokyo, 169-8555 Japan and Laboratory
for Materials Science and Technology, Waseda University, Shinjuku, Tokyo, 169-
1500 Japan
Hisanobu Wakita (407), Department of Chemistry, Faculty of Science, Fukuoka
University, ,amLakanaN Jonan-ku, Fukuoka 814-0180, Japan
O. Warsehkow (35), Dept. of Physics & Astronomy and Institute of Environmental
Catalysis Northwestern University, Evanston IL 60208
Masahiro Yamamoto (465), Department of Materials Science, Shonan Institue of
Technology, 1-1-25 Tsujido-nishikaigan, Fujisawa, 251-8511 Japan
Tomoyuki Yamamoto (199), Computational Science Division, RIKEN, 1-2 Hirosawa,
Wako-shi, Saitama 351-0198, Japan
Daisuke Yamashita(1) (263), Department of Materials Science and Engineering,
Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya
464-8603, Japan
Daisuke Yamashita(2) (399, 419, 453), Department of Materials Science and
Engineering, Waseda University, Shinjuku, Tokyo, 169-8555 Japan
Takushi Yokoyama (407), Department of Chemistry, Faculty of Science, Kyushn
University, Ropponmatsu, Chuo-ku, Fukuoka 810-8560, Japan
Hiroshi Yukawa (263, 315), Department of Materials Science and Engineering,
Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya
464-8603, Japan
Yukio Yutoh (465), Department of Materials Science, Shonan Institute of ,ygolonhceT
1-1-25 Tsujido-nishikaigan, Fujisawa, 251-8511 Japan
Preface
The Discrete Variational Xa (DV-XcQ molecular orbital calculation method is
one of the most versatile methods for estimating the electronic structures of
atom-aggregates or clusters at both ground and excited states. Also, the DV-
Xa method has been extensively used for solid-state chemistry and physics,
materials science, and electron- and X-ray spectroscopy with great success.
This is the third volume in a series of DV-Xa activities and includes a
selection of papers presented at the third international workshop and at the
fourteenth annual meeting of "DV-Xa" held at RIKEN, Wako, Japan, from
July 31 to August 3,2001. The first and second volumes on DV-Xct activities
were published in 1997 in Advances in Quantum Chemistry (Vol. 29) with the
subtitle Electronic Structure of Clusters, and in 2000 in Advances ni Quantum
Chemistry (Vol. 37) with the subtitle DV-Xa for Atomic Spectroscopy and
Materials Science.
The third international workshop on the DV-Xa method was devoted to
discussions of (1) Present and Future Applications, (2) Atomic Spectroscopy,
(3) Materials Science and (4) Future Development, in which 23 invited papers
were presented. The fourteenth annual meeting had 52 poster papers, which
were presented in 8 Sessions, i.e. Materials Science (1,2,3), Surfaces, Bound-
aries and Defects (1,2), Organic and Inorganic Compounds (1) and Spec-
troscopy (1,2). Fruitful discussions were held and the marvelous results shown
in the workshop and the annual meeting are summarized in this volume.
Finally, special thanks should be expressed to Drs. .T Ebisuzaki, .J Onoe
and .T Yamamoto (RIKEN) for providing a guesthouse for the guest speakers,
a lecture hall and the necessary facilities in RIKEN. The financial support
of RIKEN, National Institute for Materials Science, TDK, Toshiba, Kobe
Steel, Riken Keiki, Hitachi and Sankyou Publishing is also much appreciated,
and made it possible to invite ten excellent scientists from abroad. The great
success of this meeting was in great part due to the self-sacrificing effort of
Dr. .T Ishii.
Tot~o, August 20, 2002 H. Adachi, M. Uda and H. Wakita
Chairpersons
The Third International Workshop on DV-Xct
and The Fourteenth Annual Meeting on DV-Xa
iivx
Many-electron theory for electronic transition process
- Its importance in materials science -
Hirohiko Adachi and Kazuyoshi Ogasawara
Department of Materials Science and Engineering, Kyoto University
(Received June 6, 2002; in final form June 18, 2002)
The newly developed discrete variational multi-electron(DV-ME) method has
been applied to the problem of electronic transition process where the many-electron
theory is indispensable. The computational procedure of DV-ME method has been
described in some details. The application of the method to the analysis of x-ray
absorption near edge structure (XANES) from transition metal oxides has been made.
We have also performed theoretical analysis for ultraviolet absorption spectrum from
lanthanide doped metal fluoride crystal. The multiplet splitting and configuration
interaction are substantial in calculating the theoretical spectrum. The importance of
configuration interaction has been manifested in reproducing the 3d transition metal L2, 3
XANES. For the analysis of charge-transfer type compound, multiexcitation due to the
transition from ligand to metal orbitals has effectively been taken into account in the
calculation to give the satellite peak observed in the experimental spectrum. The optical
absorption spectra of tanthanide ion caused by 4f-5d transition have been calculated to
demonstrate a good agreement with the experiment, indicating the effectiveness of the
present method for new materials design and development.
KEYWORDS: many-electron theory, relativistic DV-ME method, CI calculation,
x-ray absorption, UV absorption, relativistic DV-Xct method
e-mail: adachi@ cms.mtl.kyoto-u.ac.jp
ADVANCES N1 QUANTUM CHEMISTRY, VOLUME 42
© 2003 Elsevier Science (USA). All rights reserved
0065-3276/03 $35.00
2 okihoriH Adachi dna Kazuyoshi arawasagO
I. Introduction
In the field of materials science, the quantum mechanical calculation of electronic
states has gained increased importance, since it is helpful not only for deep
understanding of various basic properties of materials, but also for design and
development of many kinds of new materials. For the electronic state calculation, the
molecular orbital method like discrete variational Xtx(DV-Xtx) method )1 and band
stnlcture calculation methods such as plane-wave-basis pseudopotential (PWPP)
method ,)2 full potential linearized augmented plane wave (FLAPW) method )3 and
orthogonalized linear combination of atomic orbitals (OLCAO) method )4 have been
proved to be very efficient to provide accurate electronic structure and chemical
bonding. These approaches have been employed to solve various problems of materials
science.
In the study of the properties of practical materials, it is very important to
understand "localized quantum structure", that is, the local atomic arrangement and the
localized electronic state and chemical bonding at very small space around surface,
interface and lattice defects such as atomic vacancy and impurity. For this problem,
recently developed experimental techniques such as high-resolution electron microscope
and various electron and x-ray spectroscopies are efficient. In order to analyze these
experiments correctly, accurate information on electronic state and chemical bonding is
necessary. The first-principles electronic state calculations by the molecular orbital
method and the band theory above described have been proved to be very useful for
these purposes. However, there are some difficult problems, which cannot be solved by
the above theoretical approaches of the one-electron model, and a more precise and
detailed analysis is required to understand the experimental results. Therefore, the first-
principles calculation of many-electron theory like configuration interaction (CI)
method should be employed to solve the problems.
We have recently developed a new theoretical method of the first-principles CI
type of calculation for many-electron systems, which we call discrete variational multi-
electron (DV-ME) method .)6's In the present paper, we have applied it to the theoretical
analyses of x-ray absorption near edge structure (XANES) for transition metal oxides ,)7
including the charge-transfer type oxides. The importance of many-electron theory and
the effectiveness of DV-ME method are demonstrated. The many-electron theory is
Many Electron Theory for Electronic Transition Process 3
also substantial for the study of optical spectrum in UV/visible region. The theoretical
analysis of the optical absorption spectra for laser materials has been made by DV-ME
metJhod. The ultraviolet absorption spectra due to f-d transitions of lanthanide ions have
been calculated and discussed.
2. ,Computational method
Usually the first principles calculation of electronic structure is made within the
one-electron theory of self-consistent-field approximation by Hatree-Fock model or
density functional theory. However, these approaches are generally insufficient to
represent accurate electronic states for many-electron systems. Then more accurate
theoretical approach like configuration interaction type of calculation is necessary.
For many-electron theory, some semiempirical methods such as crystal-field
theory and ligand-field theory have already been established. These theories are useful
for l~heoretical analysis of well-known materials, but are not very efficient for unknown
materials because some empirical parameters from experiment are necessary in the
calculation. Therefore, a first-principles method is indispensable for new materials
design and development.
As the eigenfunction of many-electron Hamiltonian for open shell configuration,
H= - -~V ~-. + ~ , (1)
v w j>il I J I
the wave function h u can be expressed not by a single Slater determinant as in the one-
electron model, but by a linear combination of Slater determinants written by
Wa(r '1 r2," ..... 'rn) = ~ aeW Oe( r '1 r2,' ..... 'rn)' (2)
where ~ is the Slater determinant. Then, the Slater determinant is the basis in this case.
The Slater determinant is formed by a combination of products of molecular orbitals
and written as
~t = ~e~(rl) ~¢l(r2) ...... ~el(rn)
0t2 (r )z ~t2(r2 ) ...... ~r2(rn )
...... (3)
r(ne~( 1 ) )2r(nt~( ...... r(nt~( )n