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Highlights in Theoretical Chemistry 9
Series Editors: Christopher J. Cramer · Donald G. Truhlar

Ron Shepard
Russell M. Pitzer
Thom Dunning Editors

Isaiah Shavitt
A Memorial Festschrift from Theoretical Chemistry
Accounts
Highlights in Theoretical Chemistry
Vol. 9
Series Editors: Christopher J. Cramer • Donald G. Truhlar

More information about this series at http://www.springer.com/series/11166

Ron Shepard • Russell M. Pitzer • Thom Dunning
Volume Editors

,VDLDK6KDYLWW
$0HPRULDO)HVWVFKULIWIURP7KHRUHWLFDO
&KHPLVWU\$FFRXQWV

With contributions from

Aleksey B. Alekseyev • Ibon Alkorta • Shigeko Asai • George B. Bacskay
Mario Barbatti • Rodney J. Bartlett • Charles W. Bauschlicher Jr.
Michael J. Bearpark • Scott R. Brozell • Robert J. Buenker
Joachim Burgdörfer • Petr Čársky • Daniel M. Chipman • Roman Čurík
Rathawat Daengngern • Janet E. Del Bene • Thom H. Dunning Jr.
José Elguero • Walter C. Ermler • Nathan D. Erxleben • Peter Funke
Gergely Gidofalvi • Friedrich Grein • Yundong Guo • Supa Hannongbua
Yanjun Hao • Frank E. Harris • James F. Harrison • Miho Hatanaka
So Hirata • Mark R. Hoffmann • Shawn Horn • Amir Karton
Jacek Karwowski • Gary S. Kedziora • Khanittha Kerdpol
Manoj K. Kesharwani • Zhuangfei Kou • Stefan Krebs • Nawee Kungwan
Benjamin G. Levine • Xiangzhu Li • Florian Libisch
Heinz-Peter Liebermann • Wenjian Liu • Hans Lischka • Victor F. Lotrich
Rahul Maitra • Jan M.L. Martin • Todd J. Martínez • Spiridoula Matsika
Rei Matsuzaki • David A. Mazziotti • Stephen L. Meloni
David Mendive-Tapia • Robert W. Molt Jr. • Debashis Mukherjee
Thomas Müller • Josef Paldus • Ajith Perera • Robin A. Phillips
R.M. Pitzer • Felix Plasser • Alessandra Ricca • Michael A. Robb
Nicholas C. Rubin • Henry F. Schaefer • Sangita Sen • Ron Shepard
Debalina Sinha • Tyler Y. Takeshita • Jeffrey L. Tilson • Iogann Tolbatov
Joseph J. Urban • Morgane Vacher • Aaron M. Virshup
C. William McCurdy • Henryk A. Witek • Yaoming Xie • Lu T. Xu
Satoshi Yabushita • Li-Juan Yu • Meiling Zhang • Zhiyong Zhang
S.C. Zimmerman
Volume Editors
Ron Shepard Russell M. Pitzer
Chemical Sciences and Engineering Division Ohio State University
Argonne National Laboratory Columbus, OH, USA
Argonne, IL, USA

Thom Dunning
National Center for Supercomputing
Applications (NCSA)
Urbana, IL, USA

Originally published in Theor Chem Acc, Volume 133 (2014),

© Springer-Verlag Berlin Heidelberg 2014

ISSN 2194-8666 ISSN 2194-8674 (electronic)

Highlights in Theoretical Chemistry
ISBN 978-3-662-48147-9 ISBN 978-3-662-48148-6 (eBook)
DOI 10.1007/978-3-662-48148-6
Library of Congress Control Number: 2015953006

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Contents

Isaiah Shavitt: Computational chemistry pioneer ...................................................... 1

S.C. Zimmerman, R.M. Pitzer

Wave function analysis with Shavitt graph density in the graphically

contracted function method .......................................................................................... 9
Gergely Gidofalvi, Scott R. Brozell, Ron Shepard

Aspects of size extensivity in unitary group adapted multireference

coupled cluster theories: the role of cumulant decomposition of spin-free
reduced density matrices ............................................................................................... 21
Rahul Maitra, Debalina Sinha, Sangita Sen, Debashis Mukherjee

Unitary group approach to the many-electron correlation problem:

spin-dependent operators .............................................................................................. 45
Xiangzhu Li, Josef Paldus

Efficient evaluation of exchange integrals by means of Fourier transform

of the 1/r operator and its numerical quadrature ....................................................... 61
Petr ýársky, Roman ýurík

The Wuppertal multireference configuration interaction (MRD-CI)

program system .............................................................................................................. 69
Robert J. Buenker, Robin A. Phillips, Stefan Krebs, Heinz-Peter Liebermann,
Aleksey B. Alekseyev, Peter Funke

Finite-temperature full configuration interaction ...................................................... 81

Zhuangfei Kou, So Hirata

Massively parallel spin–orbit configuration interaction ............................................ 91

Jeffrey L. Tilson, Walter C. Ermler

Spin–orbit DFT with analytic gradients and applications to heavy element

compounds ...................................................................................................................... 101
Zhiyong Zhang

Atomic three- and four-body recurrence formulas and related summations .......... 109
Frank E. Harris

Biconfluent Heun equation in quantum chemistry: Harmonium

and related systems ........................................................................................................ 117
Jacek Karwowski, Henryk A. Witek

Construction of complex STO-NG basis sets by the method of least squares

and their applications..................................................................................................... 129
Rei Matsuzaki, Shigeko Asai, C. William McCurdy, Satoshi Yabushita

SDS: the ‘static–dynamic–static’ framework for strongly correlated electrons ...... 141
Wenjian Liu, Mark R. Hoffmann

v
vi Contents

Singlet–triplet separations of di-radicals treated by the DEA/DIP-EOM-CCSD

methods ........................................................................................................................... 153
Ajith Perera, Robert W. Molt Jr., Victor F. Lotrich, Rodney J. Bartlett

Comparison of one-dimensional and quasi-one-dimensional Hubbard models

from the variational two-electron reduced-density-matrix method .......................... 167
Nicholas C. Rubin, David A. Mazziotti

Anchoring the potential energy surface for the Br + H2O ĺ HBr + OH reaction .. 177
Meiling Zhang, Yanjun Hao, Yundong Guo, Yaoming Xie, Henry F. Schaefer

Performance of density functionals for computation of core electron binding

energies in first-row hydrides and glycine ................................................................... 187
Iogann Tolbatov, Daniel M. Chipman

Why edge inversion? Theoretical characterization of the bonding

in the transition states for inversion in FnNH(3–n) and FnPH(3–n) (n = 0–3) ................ 195
Lu T. Xu, Tyler Y. Takeshita, Thom H. Dunning Jr.

A comparison of singlet and triplet states for one- and two-dimensional

graphene nanoribbons using multireference theory ................................................... 209
Shawn Horn, Felix Plasser, Thomas Müller, Florian Libisch, Joachim Burgdörfer,
Hans Lischka

Mechanisms of f–f hypersensitive transition intensities of lanthanide

trihalide molecules: a spin–orbit configuration interaction study ............................ 219
Miho Hatanaka, Satoshi Yabushita

A Hirshfeld interpretation of the charge, spin distribution and polarity

of the dipole moment of the open shell (3Ȉ–) phosphorus halides: PF and PCl ........ 235
James F. Harrison

Loss of a C2Hn fragment from pyrene and circumcoronene ...................................... 245

Charles W. Bauschlicher Jr., Alessandra Ricca

Heats of formation of the amino acids re-examined by means of W1-F12

and W2-F12 theories ...................................................................................................... 251
Amir Karton, Li-Juan Yu, Manoj K. Kesharwani, Jan M.L. Martin

Quantum chemical characterization of the X~(1A1), a~(3B1), A~(1B1) and B~(21A1)

states of diiodomethylene and the enthalpies of formation of diiodomethylene,
iodomethylene and iodomethylidyne ............................................................................ 267
George B. Bacskay

Theoretical studies of the excited states of p-cyanophenylalanine

and comparisons with the natural amino acids phenylalanine and tyrosine ........... 277
Stephen L. Meloni, Spiridoula Matsika

Trihalide cations MF3+, MCl3+ and MBr3+, M = B, Al, Ga: pseudo Jahn–Teller
coupling, electronic spectra and ionization potentials of MX3................................... 291
Friedrich Grein

Anomeric effects in fluoro and trifluoromethyl piperidines: a computational

study of conformational preferences and hydration ................................................... 301
Nathan D. Erxleben, Gary S. Kedziora, Joseph J. Urban
Contents vii

ı–ı and ı–S pnicogen bonds in complexes H2XP:PCX, for X = F, Cl, OH,
NC, CN, CCH, CH3, and H............................................................................................ 315
Janet E. Del Bene, Ibon Alkorta, José Elguero

The second-order Ehrenfest method a practical CASSCF approach

to coupled electron–nuclear dynamics ......................................................................... 325
Morgane Vacher, David Mendive-Tapia, Michael J. Bearpark, Michael A. Robb

Steric and electrostatic effects on photoisomerization dynamics using QM/MM

ab initio multiple spawning ........................................................................................... 337
Aaron M. Virshup, Benjamin G. Levine, Todd J. Martínez

Effects of the second hydration shell on excited-state multiple proton transfer:

dynamics simulations of 7-azaindole: (H2O)1–5 clusters in the gas phase ................. 349
Nawee Kungwan, Khanittha Kerdpol, Rathawat Daengngern, Supa Hannongbua,
Mario Barbatti
Theor Chem Acc (2014) 133:1488
DOI 10.1007/s00214-014-1488-3

OVERVIEW

Isaiah Shavitt: Computational chemistry pioneer

S. C. Zimmerman • R. M. Pitzer

Received: 24 March 2014 / Accepted: 28 March 2014 / Published online: 27 April 2014
 Springer-Verlag Berlin Heidelberg 2014

Abstract Isaiah (Shi) Shavitt (1925–2012) was a pioneer 1 Introduction

in using digital computers to study chemical problems.
From the days of vacuum tube computers with no floating
point arithmetic to the days of massively powerful com-
puters, he showed how we could solve otherwise intracta-
ble chemical problems by making use of computers. He
started with a statistical mechanical problem and soon
switched to quantum mechanical problems. He and his
associates showed how the configuration interaction
method worked, both in terms of advantages and difficul-
ties. An early problem was the effect of tunneling on
kinetics calculations on an H3 potential energy surface.
Later problems included the p-electron excited states of
benzene and the lowest excited state of methylene. He
showed how spin-eigenfunctions could be used efficiently
in configuration interaction calculations instead of Slater Isaiah (Shi) Shavitt was born in Poland in 1925, immi-
determinants. His leadership led to the Columbus suite of grated to Palestine at a very early age, and was raised in
programs put together with many collaborators. Haifa. He was educated at the Technion and Cambridge
University, earning a PhD in 1957. As a graduate student,
Keywords Computational chemistry history  Isaiah he learned to use digital computers. He soon set an
Shavitt  Configuration interaction  Electron correlation  example by using high standards in computational work
Graphical Unitary Group Approach  COLUMBUS and in writing about and evaluating such work. He per-
Programs formed very careful calculations to extend and evaluate the
method of configuration interaction for molecules. He
wrote many extensive review articles on this method and
its evaluation and co-authored a book on electron
Published as part of the special collection of articles dedicated
to the memory of Professor Isaiah Shavitt and celebrating correlation.
his many contributions.

S. C. Zimmerman
2 Family
Department of Chemistry, University of Illinois, 600 S. Mathews
Ave., Urbana, IL 61801, USA
Isaiah (Shi) Shavitt (né Kruk) was born to Zvi and Chava
R. M. Pitzer (&) Kruk on July 29, 1925, in Kutno, Poland. In 1926, his
Department of Chemistry and Biochemistry, The Ohio State
father immigrated to Palestine to establish a new life for his
University, 100 W. 18th Ave., Columbus, OH 43210, USA
e-mail: pitzer.3@osu.edu family in Haifa. In 1929, his wife and son joined him there.

Reprinted from the journal 1 123


Later, Shi changed his last name to Shavitt, which in
Hebrew means comet.
In 1957, Shi married Vera Neuwirth. Shi often said that
the best decision of his life was marrying Vera. They had a
daughter, Sharon, who married Steve Zimmerman. Both
Sharon and Steve have faculty positions at the University
of Illinois, starting in 1987 and 1985, respectively. They
have two daughters, Arielle and Ellie.
3 Career
Shi studied chemical engineering at the Technion (Israel
Institute of Technology) during 1945–1951. His studies
were interrupted by his service during 1948–1949 in
Israel’s War of Independence. Shi completed his BSc in
1950 and a Diploma in Engineering a year later, both
degrees in Chemical Engineering. He then decided to
change to theoretical chemistry and was awarded a British
Council Scholarship for Study in Britain to do so. He
earned his PhD at University of Cambridge in 1957 and
then returned to Israel. In his graduate work, he learned
computing on the EDSAC I, a primitive vacuum tube
computer that frequently required repeating calculations
just to ensure they were correct.
Short-term positions followed as a postdoctoral fellow at
the University of Wisconsin, a teaching position at Bran-
deis University, and a staff position at IBM Watson
Laboratory.
Long-term positions ensued. In 1962, he accepted a
faculty position at Technion, where he established his
research program and worked with several graduate stu-
dents. Then in 1967 he accepted a position as Research
Leader in the newly formed theoretical chemistry group at
Battelle Memorial Institute in Columbus, Ohio, adding an
adjunct professor position in the Chemistry Department at
Ohio State University a year later. After several years in
Columbus, Shi and Vera became US citizens. In 1981, he
left Battelle and became full time on the Ohio State Uni-
versity faculty. He retired at the end of 1994.
4 Postretirement science
In September 1995, Shi and the memory of his PhD
advisor, S. F. Boys, were jointly recognized by a confer-
ence in their names at St. Catharine’s College at Cam-
bridge University. Papers from this conference were
gathered in a festschrift [1], which included a paper
describing the Shavitt research group’s work up until that
time. Some of the attributes of this work were described [1]
as follows, ‘‘In an often skeptical community, his results
have the highest credibility. It is well-known that questions
123
Theor Chem Acc (2014) 133:1488
of numerical accuracy and stability are always addressed in
his work and that he has instilled his standards in his stu-
dents and colleagues.’’ He was also noted [1] for his many
carefully done review articles, particularly nos. 11, 39, 66,
and 83 in his list of publications in the ‘‘Appendix.’’
He continued his work in retirement, including detailed
studies of the energy and dipole-moment surfaces of the
water molecule (no. 90), studies of the solvated proton in
water (nos. 92, 93), a description of the COLUMBUS
programs (many collaborators, no. 94), describing the
computer program system inspired by his unitary-group
work, studies of DNA base-pair binding (no. 100. 103), and
finally, a book with R. J. Bartlett (no. 104), describing the
theory and use of many-body methods in describing elec-
tron correlation in molecules. He spent several years
working on this book, during which he first sought equa-
tion-writing and diagram-producing software that met his
exacting standards for the manuscript.
In summarizing one component of Shi’s scholarly
impact, T. H. Dunning, Director of the National Center for
Supercomputer Applications (NCSA), recently noted, ‘‘It
was Shi and his generation that laid the foundation for the
use of digital computers to obtain rigorous solutions of the
electronic Schroedinger equation.’’
5 Final years
With their daughter Sharon and her husband Steve Zim-
merman both having faculty positions at the University of
Illinois, the Shavitts decided to obtain a second house near
them in order to increase their family enjoyment and sup-
port. After several years of splitting their time between the
locations, the Shavitts sold their Columbus house in 2001
and stayed full time in Illinois. Shi was appointed Adjunct
Professor of Chemistry at the University of Illinois in 1996.
Shi enjoyed completing the New York Times crossword
puzzle daily, loved traveling, limericks, and the poems of
Ogden Nash. He was an extraordinary scholar and intellect,
but humble, generous, and kind in his interactions with
students, colleagues, and anyone he met. He is remembered
as a loving and supportive husband and father, and a doting
grandfather. After fighting disease for several years, Shi
Shavitt died December 8, 2012.
Appendix
Publications of Isaiah Shavitt
1. S. F. Boys, G. B. Cook, C. M. Reeves, and I. Shavitt,
Automatic Fundamental Calculation of Molecular
Structure, Nature, 178, 1207–1209 (1956).
2 Reprinted from the journal
Theor Chem Acc (2014) 133:1488
2. I. Shavitt and S. F. Boys, A General Expression for
Intermolecular Potentials, Nature, 178, 1340 (1956).
3. S. F. Boys, I. Jones, and I. Shavitt, Quelques
Problèmes et Résultats de Prévision de Propriétés
Moléculaires Fondamentales par le Calcul Automa-
tique, in Calcul des Fonctions d’Onde Moléculaire
(Colloques Internationaux du Centre National de la
Recherche Scientifique) (R. Daudel, editor), 82,
C.N.R.S., Paris (1958), pp. 253–261.
4. S. F. Boys and I. Shavitt, A Fundamental Calculation
of the Energy Surface for the System of Three
Hydrogen Atoms, University of Wisconsin Naval
Research Laboratory Report WIS-AF-13 (1959).
5. I. Shavitt, The Tunnel Effect Correction to the Rates
of Reactions with Parabolic and Eckart Barriers,
University of Wisconsin Theoretical Chemistry
Laboratory Report WIS-AEC-23 (1959).
6. I. Shavitt, A Calculation of the Rates of the Ortho-
Para Conversions and Isotope Exchanges in Hydro-
gen, J. Chem. Phys. 31, 1359–1367 (1959).
7. S. F. Boys and I. Shavitt, Intermolecular Forces and
Properties of Fluids. I. The Automatic Calculation of
Higher Virial Coefficients and Some Values of the
Fourth Coefficient for the Lennard-Jones Potential,
Proc. Roy. Soc. London, A254, 487–498 (1960).
8. S. F. Boys and I. Shavitt, Intermolecular Forces and
Properties of Fluids. II. A General Functional
Representation of Intermolecular Potentials and
Some Values of the 2nd, 3rd, and 4th Virial
Coefficients for Systematically Differing Potentials,
Proc. Roy. Soc. London, A254, 499–506 (1960).
9. I. Shavitt and M. Karplus, Multicenter Integrals in
Molecular Quantum Mechanics, J. Chem. Phys. 36,
550–551 (1962).
10. M. Karplus and I. Shavitt, Multicenter Pi-Electron
Integrals for the Benzene Molecule, J. Chem. Phys.
38, 1256–1257 (1963).
11. I. Shavitt, The Gaussian Function in Calculations of
Statistical Mechanics and Quantum Mechanics,
Meth. Comput. Phys. 2, 1–45 (1963).
12. I. Shavitt and M. Karplus, Gaussian Transform
Method for Molecular Integrals. I. Formulation for
Energy Integrals, J. Chem. Phys. 43, 398–414
(1965).
13. U. Kaldor and I. Shavitt, LCAO-SCF Computations
for Hydrogen Peroxide, J. Chem. Phys. 44,
1823–1829 (1966).
14. U. Kaldor and I. Shavitt, LCAO-SCF Computations
for Ammonia, J. Chem. Phys. 45, 888–895 (1966).
15. U. Kaldor and I. Shavitt, LCAO-SCF Computations
for Ethylene, J. Chem. Phys. 48, 191–203 (1968).
16. Z. Gershgorn and I. Shavitt, The Construction of
Symmetry Adapted Functions in Configuration
Reprinted from the journal
Interaction Calculations for Molecules with One
Principal Axis of Symmetry, Int. J. Quantum Chem.
Symp. 1, 403–417 (1967).
17. I. Shavitt, R. M. Stevens, F. L. Minn, and M.
Karplus, Potential Energy Surface for H3, J. Chem.
Phys. 48, 2700–2713 (1968).
18. Z. Gershgorn and I. Shavitt, An Application of
Perturbation Theory Ideas in Configuration Interac-
tion Calculations, Int. J. Quantum Chem. 2, 751–759
(1968).
19. A. Pipano and I. Shavitt, Convergence Studies and
the Selection for Configuration Functions in Config-
uration Interaction Calculations, Int. J. Quantum
Chem. 2, 741–749 (1968).
20. I. Shavitt, A Correlation of Experimental Rate
Constants of the Hydrogen Exchange Reactions with
a Theoretical H3 Potential Surface, Using Transition
State Theory, J. Chem. Phys. 49, 4048–4056 (1968).
21. M. Rubinstein and I. Shavitt, Theoretical Study of
the Potential Surface for the H4 System by Double-
Zeta Configuration Interaction Calculations, J.
Chem. Phys. 51, 2014–2024 (1969).
22. A. Pipano, R. R. Gilman, C. F. Bender, and I.
Shavitt, Ab Initio Calculation of the Inversion
Barrier in Ammonia, Chem. Phys. Lett. 5, 583–584
(1970).
23. A. Pipano, R. R. Gilman, and I. Shavitt, Invariance
of Inner Shell Correlation Energy with Geometry
Changes in a Polyatomic Molecule, Chem. Phys.
Lett. 5, 285–287 (1970).
24. I. Shavitt, Modification of Nesbet’s Algorithm for
the Iterative Evaluation of Eigenvalues and Eigen-
vectors of Large Matrices, J. Comput. Phys. 6,
124–130 (1970).
25. C. F. Bender and I. Shavitt, An Iterative Procedure
for the Calculation of the Lowest Real Eigenvalue
and Eigenvector of a Non-Symmetric Matrix, J.
Comput. Phys. 6, 146–149 (1970).
26. R. P. Hosteny, R. R. Gilman, T. H. Dunning, Jr., A.
Pipano, and I. Shavitt, Comparison of Slater and
Contracted Guassian Basis Sets in SCF and CI
Calculations of H2O, Chem. Phys. Lett. 7, 325–328
(1970).
27. J. Paldus, J. Čı́žek, and I. Shavitt, Correlation
Problems in Atomic and Molecular Systems, IV.
Extended Coupled-Pair Many-Electron Theory and
Its Application to the BH3 Molecule, Phys. Rev. A. 5,
50–67 (1972).
28. I. Shavitt, C. F. Bender, A. Pipano, and R. P. Host-
eny, The Iterative Calculation of Several of the
Lowest or Highest Eigenvalues and Corresponding
Eigenvectors of Very Large Symmetric Matrices, J.
Comput Phys. 11, 90–108 (1973).
3 123

29. T. H. Dunning, Jr., R. P. Hosteny, and I. Shavitt,
Low-Lying p-Electron States of trans-Butadiene, J.
Am. Chem. Soc. 95, 5067–5068 (1973).
30. P. J. Hay and I. Shavitt, Large-Scale Configuration
Interaction Calculations on the p-Electron States of
Benzene, Chem. Phys. Lett. 22, 33–36 (1973).
31. P. J. Hay and I. Shavitt, Ab Initio Configuration
Interaction Studies of the p-Electron States of
Benzene, J. Chem. Phys. 60, 2865–2877 (1974).
32. L. R. Kahn, P. J. Hay, and I. Shavitt, Theoretical
Study of Curve Crossing: Ab Initio Calculations on
the Four Lowest 1R? States of LiF, J. Chem. Phys.
61, 3530–3546 (1974).
33. R. P. Hosteny, T. H. Dunning, Jr., R. R. Gilman, A.
Pipano, and I. Shavitt, Ab Initio Study of the p-
Electron States of trans-Butadiene, J. Chem. Phys.
62, 4764–4779 (1975).
34. B. J. Rosenberg and I. Shavitt, Ab Initio SCF and CI
Studies on the Ground State of the Water Molecule.
I. Comparison of CGTO and STO Basis Sets near the
Hartree–Fock Limit, J. Chem. Phys. 63, 2162–2174
(1975).
35. I. Shavitt, B. J. Rosenberg, and S. Palalikit, Com-
parison of Configuration Interaction Expansions
Based on Different Orbital Transitions, Int. J. Quan-
tum Chem. Symp. 10, 33–46 (1976); erratum, ibid.
11, 651 (1977).
36. I. Shavitt, Computers and Quantum Chemistry, in
Computer Science and Scientific Computing (J.
M. Ortega, editor), Academic Press (1976),
pp. 227–253.
37. B. J. Rosenberg, W. C. Ermler, and I. Shavitt, Ab
Initio SCF and CI Studies on the Ground State of the
Water Molecule. II. Potential Energy and Property
Surfaces, J. Chem. Phys. 65, 4072–4080 (1976).
38. R. C. Raffenetti, K. Hsu, and I. Shavitt, Selection of
Terms for a CI Wavefunction to Preserve Potential
Surface Features, Theor. Chim. Acta 45, 33–44
(1977).
39. I. Shavitt, The Method of Configuration Interaction,
in Methods of Electronic Structure Theory (Modern
Theoretical Chemistry, Vol 3) (H. F. Schaefer III,
editor), Plenum Press, New York (1977),
pp. 189–275.
40. I. Shavitt, Graph Theoretical Concepts for the
Unitary Group Approach to the Many-Electron
Correlation Problem, Int. J. Quantum Chem. Symp.
11, 131–148 (1977).
41. R. J. Bartlett and I. Shavitt, Determination of the
Size-Consistency Error in the Single and Double
Excitation Configuration Interaction Model, Int.
J. Quantum Chem. Symp. 11, 165–173 (1977);
erratum, ibid. 12 543–544 (1978).
123
Theor Chem Acc (2014) 133:1488
42. R. J. Bartlett and I. Shavitt, Comparison of High-
Order Many-Body Perturbation Theory and Config-
uration Interaction for H2O, Chem. Phys. Lett. 50,
190–198 (1977); erratum, ibid. 57, 157–158 (1978).
43. C. W. Bauschlicher and I. Shavitt, Accurate ab initio
Calculations on the Singlet–Triplet Separation in
Methylene, J. Am. Chem. Soc. 100, 739–743 (1978).
44. I. Shavitt, Matrix Element Evaluation in the Unitary
Group Approach to the Electron Correlation Prob-
lem, Int. J. Quantum Chem. Symp. 12, 5–32 (1978).
45. I. Shavitt, The Utilization of Abelian Point Group
Symmetry in the Graphical Unitary Group Approach
to the Calculation of Correlated Electronic Wave-
functions, Chem. Phys. Lett. 63, 421–427 (1979).
46. R. J. Bartlett, I. Shavitt, and G. D. Purvis, The
Quartic Force Field of H2O Determined by Many-
Body Methods that Include Quadruple Excitation
Effects, J. Chem. Phys. 71, 281–291 (1979).
47. I. Shavitt, The Graphical Unitary Group Approach
(GUGA) to the Electron Correlation Problem-
Survey and Recent Advances, in Electron Corre-
lation: Proceedings of the Daresbury Study Week-
end, 17–18 November, 1979 (M. F. Guest and S.
Wilson, editors), Science Research Council, Dares-
bury Laboratory, Warringon, England (1980),
pp. 60–68.
48. C. W. Bauschlicher Jr. and I. Shavitt, A Low-Energy
Passage for C? ? H2 ? CH? (1R?) ? H, Chem.
Phys. Lett. 75, 62–65 (1980).
49. I. Shavitt and L. T. Redmon, Quasidegenerate
Perturbation Theories. A Canonical van Vleck
Formalism and Its Relationship to Other
Approaches. J. Chem. Phys. 73, 5711–5717 (1980).
50. C. F. Jackels and I. Shavitt, Accuracy of Energy
Extrapolation in Multireference Configuration Inter-
action Calculations, Theor. Chim. Acta 58, 81–96
(1981).
51. I. Shavitt, The Graphical Unitary Group Approach
and Its Application to Direct Configuration Interac-
tion Calculations, in The Unitary Group for the
Evaluation of Electronic Energy Matrix Elements
(Lectures Notes in Chemistry 22) (J. Hinze, editor),
Springer Verlag, Berlin (1981), pp. 51–99.
52. M. J. Redmon, R. J. Bartlett, B. C. Garrett, G.
D. Purvis III, P. M. Saatzer, G. C. Schatz, and I.
Shavitt, Collisional Excitation of H2O by O-Atom
Impact : Classical Dynamics on an Accurate ab initio
Potential Energy Surface, in Potential Energy Sur-
faces and Dynamics Calculations (D. G. Truhlar,
editor), Plenum, New York (1981), pp. 771–803.
53. H. Lischka, R. Shepard, F. B. Brown, and I. Shavitt,
New Implementation of the Graphical Unitary Group
Approach for Multireference Direct Configuration
4 Reprinted from the journal
Theor Chem Acc (2014) 133:1488
Interaction Calculations, Int. J. Quantum Chem.
Symp. 15, 91–100 (1981).
54. P. G. Lykos and I. Shavitt, editors, Supercomputers and
Chemistry (ACS Symposium Series 173), American
Chemical Society, Washington, D. C. (1981), 278 pp.
55. R. Shepard, I. Shavitt, and J. Simons, Comparison of
Convergence Characteristics of Some Iterative Wave
Function Optimization Methods, J. Chem. Phys. 76,
543–557 (1982).
56. G. Born and I. Shavitt, A Unitary Group Formulation
of Open-Shell Electron Propagator Theory, J. Chem.
Phys. 76, 558–567 (1982).
57. P. Čársky, M. Svrček, I. Hubač, F. B. Brown, and I.
Shavitt, Correlation Energy in Triplet States. Com-
parison of Many-Body Perturbation Theory and
Configuration Interaction for CH2 and O2, Chem.
Phys. Lett. 85, 17–20 (1982).
58. I. Shavitt, The Unitary Group and the Electron
Correlation Problem, in New Horizons of Quantum
Chemistry (P.-O. Löwdin and B. Pullman, editors),
Reidel, Dordrecht (1983), pp. 279–293.
59. F. B. Brown, I. Shavitt, and R. Shepard, Multirefer-
ence Configuration Interaction Treatment of Poten-
tial Energy Surfaces: Symmetric Dissociation of
H2O in a Double-Zeta Basis, Chem. Phys. Lett.105,
363–369 (1984).
60. I. Shavitt, The Treatment of Electron Correlation:
Where Do We Go From Here? in Advanced Theories
and Computational Approaches the Electronic
Structure of Molecules (C. E. Dykstra, editor),
Reidel, Dordrecht (1984). pp. 185–196.
61. I. Shavitt, Geometry and Singlet-Triplet Energy Gap
in Methylene: A Critical Review of Experimental
and Theoretical Determinations, Tetrahedron 41,
1531–1542 (1985).
62. W. C. Ermler, B. J. Rosenberg, and I. Shavitt, Ab
Initio SCF and CI Studies on the Ground State of the
Water Molecule. III. Vibrational Analysis of Poten-
tial Energy and Property Surfaces, in Comparison of
Ab Initio Quantum Chemistry with Experiment: State
of the Art (R. J. Bartlett, editor), Reidel, Dordrecht
(1985), pp. 171–215.
63. D. C. Comeau, R. J. Zellmer, and I. Shavitt, The
Location and Characterization of Stationary Points
on Molecular Potential Energy Surfaces, in Geomet-
rical Derivatives of Energy Surfaces and Molecular
Properties (P. Jørgensen and J. Simons, editors),
Reidel, Dordrecht (1986), pp. 243–251.
64. I. Shavitt, F. B. Brown, and P. G. Burton, Configu-
ration Selection and Extrapolation in Multireference
Configuration Interaction Calculations: The (H2)2 van
der Waals Complex as a Benchmark Example, Int.
J. Quantum Chem. 31, 507–520 (1987).
Reprinted from the journal
65. R. J. Barlett, S. J. Cole, G. D. Purvis, W. C. Ermler,
H. C. Hsieh, and I. Shavitt, The Quartic Force Field
of H2O Determined by Many-Body Methods. II.
Effects of Triple Excitations, J. Chem. Phys. 87,
6579–6591 (1987).
66. I. Shavitt, Unitary Group Approach to Configuration
Interaction Calculations of the Electronic Structure
of Atoms and Molecules, in Mathematical Frontiers
in Computational Chemical Physics (D. G. Truhlar,
editor), Springer-Verlag, Berlin (1988), pp. 300–349.
67. R. Ernenwein, M. Benard, and I. Shavitt, Vectorizing
a Sequence of Conditional Branches: the Calculation
of the Class Index of Two-Electron Repulsion
Integrals on Cray Computers, Comput. Phys. Com-
mun. 48, 175–180 (1988).
68. R. Shepard, I. Shavitt, R. M. Pitzer, D. C. Comeau,
M. Pepper, H. Lischka, P. G. Szalay, R. Ahlrichs, F.
B. Brown, and J.–G. Zhao, A Progress Report on the
Status of the COLUMBUS MRCI Program System,
Int. J. Quantum Chem. Symp. 22, 149–165 (1988).
69. D. C. Comeau, I. Shavitt, P. Jensen, and P.
R. Bunker, An ab initio Determination of the
Potential Energy Surfaces and Rotation-Vibration
Energy Levels of Methylene in the Lowest Triplet
and Singlet States and the Single-Triplet Splitting, J.
Chem. Phys. 90, 6491–6500 (1989).
70. J. E. Del Bene and I. Shavitt, Comparison of
Methods for Determining the Correlation Contribu-
tions to Hydrogen Bond Energies, Int. J. Quantum
Chem. Symp. 23, 445–452 (1989).
71. J. E. Del Bene and I. Shavitt, Comparison of
Theoretical Methods for the Determination of the
Protonation and Deprotonation Energies of NH3,
H2O, HF, PH3, H2S, HCl, and HCN, J. Phys. Chem.
94, 5514–5518 (1990).
72. J. E. Del Bene, E. A. Stahlberg, and I. Shavitt, A
Theoretical Study of the Complexes of N2O with
H?, Li?, and HF Using Various Correlation Meth-
ods, Int. J. Quantum Chem. Symp. 24, 455–466
(1990).
73. J. E. Del Bene and I. Shavitt, Comparison of
Theoretical Methods for the Determination of the
Li? Affinities of Neutral and Anionic First- and
Second-Row Bases, Int. J. Quantum Chem. Symp.
24, 365–373 (1990).
74. J. E. Del Bene, K. Kim, and I. Shavitt, An ab initio
Study of Symmetry Breaking in Calculations on the
First Excited Singlet State of N2H2, Can. J. Chem.
69, 246–250, (1991).
75. J. E. Del Bene, H. D. Mettee, and I. Shavitt, The
Structure, Binding Energy, and Vibrational Frequen-
cies of CH3CN…HCl, J. Phys. Chem. 95,
5387–5388 (1991).
5 123

76. J. E. Del Bene and I. Shavitt, A Theoretical Study of
the Neutral, Protonated, and Deprotonated Trimers
of HF and HCl, J. Mol. Struct. (THEOCHEM) 234,
499–508 (1991).
77. I. Shavitt, J. E. Del Bene, and D. W. Ewing, Ab Initio
Study of Spiropentadiene, C5H4, J. Am. Chem. Soc.
113, 9389–9391 (1991).
78. R. D. Kent, M. Schlesinger, and I. Shavitt, Graphical
Unitary Group Approach to Spin–Spin Interaction,
Int. J. Quantum Chem. 41, 89–103 (1992).
79. J. E. Del Bene, D. H. Aue, and I. Shavitt, Stabilities
of Hydrocarbons and Carbocations. I. A Comparison
of Augmented 6-31G, 6-311G, and Correlation-
Consistent Basis Sets, J. Am. Chem. Soc. 114,
1631–1640 (1992).
80. I. Shavitt, The Ak and Bk Approximate CI Methods.
Comment on a Paper by Maynau and Heully, Chem.
Phys. Lett. 192, 135–137 (1992).
81. K. Kim, I. Shavitt, and J. E. Del Bene, Theoretical
Study of the Di-imide (N2H2) Molecule in Ground
and n ? p* Excited States, J. Chem. Phys. 96,
7573–7579 (1992).
82. D. W. Ewing and I. Shavitt, Double Zeta Basis Sets
in Carbon Cluster Calculations, in Physics and
Chemistry of Finite Systems: From Clusters to
Crystals, Vol. I. (P. Jena, S. N. Khanna, and B.
K. Rao, editors), Kluwers, Dordrecht, Holland
(1992), pp. 561–567.
83. I. Shavitt, The History and Evolution of Gaussian
Basis Sets, Israel J. Chem. 33, 357–368 (1993).
84. J. E. Del Bene and I. Shavitt, Basis-Set Effects on
Computer Acid–Base Interaction Energies Using the
Dunning Correlation-Consistent Polarized Split-
Valence Basis Sets, J. Mol. Struct, (THEOCHEM)
307, 27–34 (1994).
85. J. E. Del Bene and I. Shavitt, An ab initio Study of
the Complexes of HCl with the Chloromethanes, J.
Mol. Struct. (THEOCHEM) 314, 9–17 (1994).
86. M. J. M. Pepper, I. Shavitt, P. v. R. Schleyer, M.
N. Glukhovstev, R. Janoschek, and M. Quack, Is the
Stereomutation of Methane Possible? J. Comput.
Chem. 16, 207–225 (1995).
87. L. Ojamäe, I. Shavitt, and S. J. Singer, Potential
Energy Surfaces and Vibrational Spectra of H5O2?
and Larger Hydrated Proton Complexes, Int.
J. Quantum Chem. Symp. 29, 657–668 (1995).
88. N. C. Handy, J. A. Pople, and I. Shavitt, Samuel
Francis Boys, J. Phys. Chem. 100, 6007–6016
(1996).
89. G. S. Kedziora and I. Shavitt, Calculation and
Fitting of Potential Energy and Dipole Moment
Surfaces for the Water Molecule: Fully ab initio
Determination of Vibrational Transition Energies
123
Theor Chem Acc (2014) 133:1488
and Band Intensities, J. Chem. Phys. 106,
8733–8745 (1997).
90. J. E. Del Bene and I. Shavitt, The Quest for
Reliability in Calculated Properties of Hydrogen-
bonded Complexes, in Molecular Interactions, From
van der Waals to Strongly Bound Complexes, (Wiley
Tutorial Series in Theoretical Chemistry) (S. Schei-
ner, editor), Wiley: Chichester (1997), pp. 157–179.
91. I. Shavitt, The History and Evolution of Configura-
tion Interaction, Mol. Phys. 94, 3–17 (1998).
92. L. Ojamäe, I. Shavitt, and S. J. Singer, Potential
Models for Simulations of the Solvated Proton in
Water, J. Chem. Phys. 109, 5547–5564 (1998).
93. C. V. Ciobanu, L. Ojamäe, I. Shavitt, and S.
J. Singer, Structure and Vibrational Spectra of
H?(H2O)8: Is the Excess Proton in a Symmetrical
Hydrogen Bond? J. Chem. Phys. 113, 5321–5330.
94. H. Lischka, R. Shepard, R. M. Pitzer, I. Shavitt, M.
Dallos, T. Müller, P. G. Szalay, M. Seth, G.
S. Kedziora, S. Yabushita, and Z. Zhang, High-
Level Multireference Methods in the Quantum-
Chemistry Program System COLUMBUS: Analytic
MR-CISD and MR-AQCC Gradients and MR-
AQCC-LRT for Excited States, GUGA Spin–Orbit
CI and Parallel CI Density, Phys. Chem. Chem.
Phys. 3, 664–673 (2001).
95. R. Shepard, I. Shavitt, and H. Lischka, Software
News and Updates Reducing I/O Costs for the
Eigenvalue Procedure in Large-Scale Configuration
Interaction Calculations, J. Comp. Chem. 23,
1121–1125 (2002).
96. I. Shavitt, Multi-State Multireference Rayleigh-Sch-
roedinger Perturbation Theory for Mixed Electronic
States: Second and Third Order, Int. J. Mol. Sci. 3,
639–655.
97. J.-L. Kuo, C.V. Ciobanu, L. Ojamäe, I. Shavitt, and
S. J. Singer, Short H-Bonds and Spontaneous Self-
dissociation in (H2O)20: Effects of H-Bond Topol-
ogy, J. Chem. Phys. 118, 3583–3588.
98. J. A. Karwowski and I. Shavitt, Configuration
Interaction, in Handbook of Molecular Physics and
Quantum Chemistry (S. Wilson, editor) 2, Wiley:
Chichester (2003), pp. 227–271.
99. I. Shavitt, Are Exponential-Type Basis Sets Prefer-
able to Gaussians? Int. J. Quantum Chem. 100,
105–108 (2004).
100. J. R. Quinn, S. C. Zimmerman, J. E. Del Bene, and I.
Shavitt, Does the A-T or G-C Base-Pair Possess
Enhanced Stability? Quantifying the Effects of
CH_O Interactions and Secondary Interactions on
Base-Pair Stability Using a Phenomenological Ana-
lysis and ab initio Calculations, J. Am. Chem. Soc.
129, 934–941 (2007).
6 Reprinted from the journal
Theor Chem Acc (2014) 133:1488
101. R. Shepard, G. S. Kedziora, H. Lischka, I. Shavitt, T.
Müller, P. G. Szalay, M. Kállay, and M. Seth, The
Accuracy of Molecular Bond Lengths Computed by
Multireference Electronic Structure Methods, Chem.
Phys. 349, 37–57 (2008).
102. I. Shavitt, Tribute to Russell M. Pitzer, J. Phys.
Chem. A 113, 12339–12342 (2009).
103. J. R. Quinn, S. C. Zimmerman, J. E. Del Bene, and I.
Shavitt, Prebiotic Selection of the AT Base Pair?
A Physical Organic Approach to Understanding AT
Base-Pair Stability Indicates Special Stability, in
ACS Symposium Series (2009), 1025 (Chemical
Evolution II), pp. 95–107.
104. I. Shavitt and R. J. Bartlett, Many-Body Methods in
Chemistry and Physics: MBPT and Coupled-Cluster
Theory, Cambridge University Press: Cambridge,
(2009), 532 pp.
Reprinted from the journal
105. H. Lischka, T. Müller, P. G. Szalay, I. Shavitt, R.
M. Pitzer, and R. Shepard, COLUMBUS-A Program
System for Advanced Multireference Theory Calcu-
lations, in Wiley Interdisciplinary Reviews: Compu-
tational Molecular Science 1, (2011), pp. 191–199.
106. I. Shavitt, Perspective: Björn Roos and Direct
Configuration Interaction, Int. J. Quantum Chem.
111, 3263–3266 (2011).
Reference
1. Kaldor U, Pitzer RM (1996) Isaiah Shavitt. J Phys Chem
100:6017–6022
7 123
Theor Chem Acc (2014) 133:1512
DOI 10.1007/s00214-014-1512-7
REGULAR ARTICLE
Wave function analysis with Shavitt graph density
in the graphically contracted function method
Gergely Gidofalvi • Scott R. Brozell •
Ron Shepard
Received: 11 February 2014 / Accepted: 24 May 2014 / Published online: 15 July 2014
 Springer-Verlag Berlin Heidelberg 2014
Abstract The goals of electronic structure theory are to
make quantitative predictions of molecular properties and
to provide qualitative insight into bonding as well as fea-
tures of potential energy surfaces. Oftentimes, the two
goals are at odds as an accurate treatment requires a
complicated wave function that obscures chemical insight.
The multifacet graphically contracted function (MFGCF)
method offers a new approach that allows both goals to be
addressed simultaneously. The recursive product structure
of the MFGCF wave function reduces the exponential
scaling of the exact wave function and allows the compu-
tation of molecular properties with polynomial scaling with
respect to system size. Additionally, the graph density
concept provides an intuitive tool for visualizing and ana-
lyzing the qualitative features of the wave function. In this
work, the graph densities for model systems are examined
to demonstrate their utility in analyzing the changes in
wave function character along potential energy surfaces
and near avoided crossings. Finally, we demonstrate that
the graph density exposes the structure of the exact wave
Dedicated to the memory of Professor Isaiah Shavitt and published
as part of the special collection of articles celebrating his many
contributions.
G. Gidofalvi (&)
Department of Chemistry and Biochemistry, Gonzaga
University, 502 E. Boone Ave., Spokane, WA 99258-0102, USA
e-mail: gidofalvi@gonzaga.edu
S. R. Brozell  R. Shepard
Chemical Sciences and Engineering Division, Argonne National
Laboratory, Argonne, IL 60439, USA
e-mail: srb@osc.edu
R. Shepard
e-mail: shepard@tcg.anl.gov
Reprinted from the journal
function for a system of noninteracting molecules as a
product of the fragment wave functions.
Keywords Multifacet graphically contracted function
method  Configuration interaction  Graphical unitary
group approach  Shavitt graph  Wave function analysis 
Graph density  Node density  Arc density
1 Introduction
At the heart of electronic structure theory lies the electronic
Schrödinger equation, and the ultimate goal of quantum
chemistry is the accurate and efficient computation of its
solutions: the energies and associated wave functions of the
electronic states of atoms and molecules. The graphical
unitary group approach (GUGA) of Shavitt [1–5] estab-
lishes a convenient representation for expansions of elec-
tronic wave functions in terms of spin-adapted
configuration state functions (CSFs). GUGA is based on the
unitary group approach in which an integer triple ða; b; cÞ of
a Paldus ABC tableau [6–9] defines the number of orbitals
n ¼ a þ b þ c, the number of electrons N ¼ 2a þ b, and the
spin quantum number b ¼ 2S. In GUGA, each node of a
Shavitt graph corresponds to a unique integer triple. The
Shavitt graph for a three-electron three-orbital doublet full-
CI wave function is shown in Fig. 1a. The tail node ð0; 0; 0Þ
represents the physical vacuum, and the head node repre-
sents the n, N, and S of the wave function. The vertical
levels in a Shavitt graph coincide with a specific sequence
of orbitals. The nodes between adjacent levels are con-
nected by arcs or steps, and the four possible step numbers
are d ¼ 0, 1, 2, and 3, each with ðDa; Db; DcÞ values of
ð0; 0; 1Þ, ð0; 1; 0Þ, ð1; 1; 1Þ, and ð1; 0; 0Þ respectively. Step
numbers d ¼ 0 and 3 denote empty and doubly occupied
9 123
 Theor Chem Acc (2014) 133:1512

(a) the wave function parameters. In GUGA CI, the CSF

b= 1 0 2 1 0 expansion coefficients (x) are obtained by solving the
3 (1,1,1) eigenvalue equation Hx = E x using iterative diagonal-
ization techniques [16] that rely on the efficient evaluation
and use of the Hamiltonian (H) matrix elements between
2 (1,1,0) (1,0,1) (0,2,0) (0,1,1) CSFs [4]. Although the energy and its geometrical deriv-
atives are useful in predicting equilibrium and transition
level

state structures as well as energies of reactions and barrier

1 (1,0,0) (0,1,0) (0,0,1) heights, the wave function itself is equally important as it
provides insight into the chemical and physical properties;
unfortunately, this utility of the wave function is oftentimes
0 (0,0,0) obscured by the (possibly very) large number of parame-
b= 1 0 2 1 0
ters. Thus, several techniques have been developed to
1 0 allow the efficient interpretation and visualization of
a
electronic wave functions. Most notably, the one-electron
(b) reduced density matrix (1-RDM) may be used in popula-
b= 1 0 2 1 0 tion analysis methods, such as those proposed by Mullik-
3 9 en [17] and Löwdin [18], to estimate gross atomic charges
and bond orders [19]. Relative to the canonical molecular
orbitals, the eigenvectors of the 1-RDM, the natural orbi-
2 5 6 7 8 tals, are more appropriate in some circumstances for cor-
related calculations and have been used in various CI [20–
level

24] and coupled-cluster [25–29] methods. Although chan-

1 2 3 4
0 1
b= 1 0 2 1 0
=+1.000E+00 1 0
a
Fig. 1 a Full-CI Shavitt graph for a three-electron three-orbital doublet
state. Nodes of the graph are labeled according to the integer triples
ðaj ; bj ; cj Þ. The slant of the arcs away from vertical increases with the
step number; d ¼ 0 is vertical, whereas d ¼ 3 has the largest slant.
b The graph density plot for the one-configuration SCF wave function
j/21 /12 /03 i. The orbital levels are ordered according to orbital energy and
the nodes are labeled according to the contiguous indexing scheme
j ¼ 1; . . .; Nrow , where Nrow is the number of nodes in the Shavitt graph.
Arc(node) densities with appreciable values are green, while gray
indicates arcs(nodes) with negligible densities
orbitals, respectively, while step number d ¼ 1ð2Þ corre-
sponds to a singly occupied orbital such that the cumulative
spin is increased(decreased) by Db ¼ 1. A walk along
arcs from the vacuum node to the head node defines a spin-
adapted CSF expansion term. The GUGA formulation has
been employed in several electronic structure packages for
configuration interaction (CI) and multiconfiguration self-
consistent field (MCSCF) calculations, such as GA-
MESS [10, 11] and MOLCAS [12], and notably in the
COLUMBUS Program System of Shavitt and coworkers [3,
13–15] within which the present work has been performed.
The energy (E) is of central importance in variational
electronic structure methods as a criterion for optimizing
ges in wave function character can be observed by exam-
ination of the 1-RDM matrix elements, the information
contained in the 1-RDM is highly contracted, and the
subtle details associated with spin-coupling in the wave
function are obscured.
In previous work, we introduced [30] and implemented
[31–33] a novel wave function analysis technique based on
Shavitt graphs. It is denoted as the graph density concept,
and it enables wave functions to be characterized and
compared in terms of nodes and arcs of the Shavitt graph.
The graph density technique arose in the context of our
graphically contracted function (GCF) method [30–41],
which opens up the possibility to compute astronomically
large CI expansions. For such wave functions, traditional
analysis approaches based on individual CSF coefficients
become intractable. However, the graph density concept is
generally applicable to any expansion length or form that
can be represented on a Shavitt graph. Thus, the graph
density concept offers a tool that complements existing
wave function analysis methods. Node densities contain
information related to both orbital occupations and spin-
coupling within the molecule, whereas the occupation
numbers do not contain information about spin-coupling.
For example, a singlet and triplet wave function can, in
principle, have the same natural orbitals and occupations,
whereas the graph densities of the two wave functions
would be distinct. Arc densities also contain information
that can aid the determination of the seniority quantum
number of the wave function [42]. Additionally, arc den-
sities are related to the one-orbital reduced density matrices

123 10 Reprinted from the journal

Theor Chem Acc (2014) 133:1512

introduced to study orbital interaction in density matrix coefficients scales exponentially ðOðnN ÞÞ with system size,
renormalization group theory [43] using quantum infor- the number of parameters in a GCF is proportional to the
mation theory [44, 45]. These one-orbital reduced density number of arcs in the Shavitt graph and scales polynomially
matrices may be considered as contractions of the arc ðOðN 2 nÞÞ with system size [30]. Because of the product
densities and provide useful insight into changes in elec- structure, the GCF basis function is also seen to be a matrix
tronic structure along the potential energy surface [46] and product state [48] and is similar to the wave function An-
aid in the characterization of chemical bonds [47]. satz employed in spin-adapted density matrix renormal-
After a brief review of the GCF method and the com- ization group methods [49, 50].
putation of graph densities in that context, we present wave The linear coefficients c are obtained by solving the
function analyses via graph densities along the potential generalized eigenvalue equation Hc = E Sc, where H and
energy curves for the C2v insertion pathway for BeH2 , the S are the Hamiltonian and overlap matrices evaluated in
dissociation of C2 , and D2h and D4h dissociation paths of the GCF basis [34]. The arc factors a are optimized to
H8 . The purpose of the present work is to develop the minimize the energy of a single state, or the weighted
necessary background for interpreting graph densities and average of the energies of several states [32]. Efficient
to demonstrate their utility in analyzing the wave function. routines for computing overlap and Hamiltonian matrix
Thus, to minimize the complexity, each example presented elements and evaluating derivatives of the state-specific
herein considers valence-only correlation and employs and state-averaged energies have been developed [32]. In
small basis sets that capture the essential features of the addition to enabling the efficient computation of the
wave function. Nonetheless, we emphasize that this analysis quantities needed during the optimization, the GCF energy
approach is equally applicable to arbitrary wave functions. is variational and size extensive in a localized orbital basis.
The variational flexibility of the GCF wave function may
be improved by increasing the size of the GCF expansion
2 Method basis in Eq. (1), increasing the number of facets associated
with the nodes of the Shavitt graph, or increasing both. In
Within the GCF approach, the wave function is expressed our initial work every node was restricted to a single facet,
as but preliminary results indicate that varying the number of
X
N GCF facets to form a multifacet GCF (MFGCF) while restricting
jwi ¼ cM jMi; ð1Þ NGCF to be equal to the number of electronic states of
M¼1 interest results in more flexible basis functions and in better
where each GCF jMi is a multiconfigurational function convergence [32].
formally defined as a linear combination of all the CSFs The character of the wave function may be analyzed
~ comprising the underlying CI space
jmi through the graph density concept introduced in Ref. [30].
Formally, the node density of a particular node of the
X
NCSF
Shavitt graph is equal to the sum of the squares of the CI
jMi ¼ ~
m jmi;
xM ð2Þ
m¼1
coefficients for those CSFs that pass through that node.
Thus, it is a measure of the importance of that node in
and the CSF expansion coefficients xM
m are defined as describing the wave function. Using an analogous argu-
ordered products of arc factors aM ment, the arc densities quantify the importance of indi-
vidual arcs in the wave function. In fact, since the node
M;djm ;j M;djm ;j M;djm Y
n M;djm
;jn ;jp density is the sum of the arc densities leading to that node,
m ¼ aj0 ;j1
xM aj1 ;j2 1 2 . . .ajn1 ;jn1 ¼ ajp1 ;jp1 : ð3Þ
0 1
n p
p¼1 node densities may be considered to be contractions over
M;dj ;jp
arc densities. From the formal definition of the node and
In Eq. (3), ajp1 ;jp1
p
is a real fjp1 by fjp matrix in which arc densities, it readily follows that the sum of the node
fjp1 (fjp ) is the number of facets associated with node densities within any level of the Shavitt graph and the sum
jp1 (jp ) in level p  1(p). The superscript djmp1 ;jp indicates of the arc densities connecting any two adjacent levels of
the step d that connects nodes jp1 and jp that are touched the Shavitt graph are both equal to unity for a normalized
by the CSF jmi. ~ In this way, the Shavitt graph plays a wave function. The graphical representation of the node
central role in the mathematical structure of the resulting and arc densities using graph density plots provides an
wave function and in its dependence on the nonlinear arc intuitive tool for analyzing the wave function. Within
factor parameters. It is also important to recognize that an these graphs, the magnitude of the node density is pro-
arc of the Shavitt graph is shared by a possibly large portional to the area of the circle representing the node.
number of CSFs. Thus, whereas the number of linear CSF Thus, the head and tail nodes are represented by circles

Reprinted from the journal 11 123


with unit area. Arcs with ‘‘appreciable’’ densities above
some predefined threshold are represented by green lines,
and all other arcs with small densities are represented by
gray lines. The threshold is proportional to the maximum
arc density in the normalized wave function. In this work
the thresholds were 0.001 for all graph density plots. To
illustrate the graph density concept, consider the SCF
wave function for a three-electron three-orbital molecule
that consists of a single configuration with the first orbital
doubly occupied, the second orbital singly occupied, and
the highest energy orbital empty. The graph density plot
for this wave function is shown in Fig. 1b. For such a
wave function, only those three arcs that are consistent
with this occupation pattern have appreciable arc densities
and all remaining arc densities are zero. Thus, since the
node densities are contractions over the connecting arc
densities, it is readily seen that, at each level of the Shavitt
graph, there is a single node with unit node density. Note
that for wave functions with more than one dominant
configuration, several nodes and arcs within each level of
the Shavitt graph may acquire significant densities. Thus,
a significant ‘‘spread’’ in node and arc density within a
level indicates the multiconfigurational character of the
wave function.
For a GCF expansion, the density contributions can be
determined directly from the partial overlap matrices and the
arc factors. This allows graph density analysis of wave func-
tion expansions that are much larger than could be considered
with conventional approaches that rely on explicit summa-
tions of CSF contributions. For a normalized GCF wave
function, the node density Dk may be computed as [30, 32]
X
N GCF X
N GCF h  i
MN T MN
Dk ¼ cM cN DMN
k ¼ c M c N Tr c k 
c k : ð4Þ
M;N M;N
The partial lower-walk overlap matrix cMN measures the
k
overlap of all those CSFs that lead from the vacuum node
of the Shavitt graph to node k, while the partial upper-walk
overlap matrix cMN determines the overlap of all those
k
CSFs that lead from the head node of the Shavitt graph to
node k. Since the CSF coefficients are expressed as pro-
ducts of the arc factor matrices in Eq. (3), the partial
overlap matrices may be computed recursively [30].
Assuming that every node of the Shavitt graph is charac-
terized by fmax facets, the recursive computation of all
 
k g and f
matrices fcMN cMN
k g would scale as O Nrow fmax ,
3
where Nrow is the number of nodes in the Shavitt graph and
scales as OðN 2 nÞ for full-CI wave functions. Thus, com-
puting the node densities for a GCF wave function with
NGCF expansion GCFs scales linearly with the number of
 2 
orbitals O NGCF N 2 fmax
3
n . A similar analysis in terms of
transition arc densities reveals that evaluating arc densities
with GCF wave functions has a similar scaling. It is
123
Theor Chem Acc (2014) 133:1512
noteworthy that the matrix product structure of the CSF
coefficients in Eq. (3) is not required for computing graph
densities and only facilitates their construction. Thus, the
graph density concept is equally useful in the interpretation
of traditional CI wave functions. However, in contrast to
these traditional CI expansions for which the computa-
tional cost of analysis increases exponentially with the
system size, the GCF wave function may be analyzed at
polynomial cost. Although the examples presented in this
work are small enough so that examining the qualitative
features of the wave functions from both the CSF and
graph density perspectives is tractable, the graph density
concept will afford the analysis of future GCF wave
functions for which the number of CSFs would be pro-
hibitively large. Graph densities of a given electronic state
at various points on a potential energy surface (PES) and
densities of various electronic states can be compared in
order to determine the essential differences in the wave
functions. Graph densities can be monitored along a reac-
tion path in order to characterize the changes in the wave
function associated with barriers, wells, and other PES
features.
3 Results
3.1 BeH2 C2v insertion pathway
The equilibrium geometry for collinear BeH2 and H2 , as
well as the saddle point geometry are optimized at the
complete active-space self-consistent field (CASSCF) level
using the 1a21 ð2  4a1 ; 1b1 ; 1  2b2 Þ4 active space. All
calculations employ Dunning’s cc-pVTZ basis sets [51,
52], and C2v symmetry is imposed by restricting the line
segment connecting the center of mass of H2 and Be to be
perpendicular to the H2 bond axis (Fig. 2). In terms of
(RBeH2 , RHH ), where RBeH2 is the distance between the
beryllium atom and the center of mass of molecular
hydrogen and RHH is the separation between the two
hydrogen atoms, the equilibrium geometry of collinear
BeH2 is (0:0a0 , 5:1142a0 ) and the transition state geometry
Fig. 2 Geometrical parameters Be
used to describe the potential
energy curve for the C2v inser-
tion pathway in BeH2 . The
drawing is to scale for the
transition state geometry RBe−H2
H H
RH−H
12 Reprinted from the journal
Theor Chem Acc (2014) 133:1512
is given by (2:5024a0 , 2:1507a0 ). The asymptotic H2
equilibrium bond distance is 1:4272a0 . As in Ref. [53], the
reaction path is defined as two straight-line segments in
terms of RBeH2 and RHH . The first line segment passes
through the collinear equilibrium geometry, the transition
state geometry, and (RBeH2 ; 1:4272a0 ), where RBeH2 ¼
3:1133a0 is the intersection between the two line segments.
For RBeH2  RBeH2 , the second line segment is the hori-
zontal line (RBeH2 ; 1:4272a0 ).
 
The reaction Beð1 SÞ þ H2 1 Rþ g ! BeH2 ð1 A1 Þ along
the C2v path is interesting because the 11 A1 ground state
involves the avoided crossing between the two closed-shell
configurations 1a21 2a21 3a21 and 1a21 2a21 1b22 . The former
configuration dominates at large Be  H2 separations and
corresponds to the ground-state fragments Beð1 S Þ and
 
H2 1 Rþg , while the latter configuration is dominant near
the collinear equilibrium geometry. The 21 A1 PES corre-
 
sponds to the reaction Beð1 PÞ þ H2 1 Rþ
g ! BeH2 ð1 A1 Þ.
The shape of the 21 A1 PES is more complex as it involves
three avoided crossings between the aforementioned
closed-shell configurations as well as the two open-shell
configurations 1a21 2a1 3a1 1b22 and 1a21 2a21 3a1 4a1 . Thus, a
flexible wave function expansion is necessary to describe
the qualitative features of the PESs. State-averaged full-
valence CASSCF calculations were used to optimize the
1a1 core orbital and the ð2  4a1 ; 1b1 ; 1  2b2 Þ active
orbitals. Natural orbital resolution is imposed on the active
orbital space. The subsequent state-averaged MFGCF cal-
culations with NGCF ¼ 2 are carried out using the valence
orbitals and employ the 64 full-CI Shavitt graph. The
convergence of the MFGCF energy was examined by a
sequence of calculations with a fixed maximum number of
facets, fmax , for every node of the Shavitt graph. Future
developments will explore the possibility of dynamically
adjusting the number of facets for individual nodes of the
Shavitt graph in order to satisfy overall accuracy
requirements.
For both PESs, the MFGCF energies with fmax ¼ 2 are
within 2.1 mEh of the CASSCF results, and the MFGCF
energies with fmax ¼ 4 (Fig. 3) are exact. The graph density
plots in Fig. 4 demonstrate the changes in the electronic
structure of the two lowest energy 1 A1 states. The core 1a1
orbital is excluded from the graphs. For the ground state,
the graph densities at the collinear equilibrium geometry,
RBeH2 ¼ 0a0 , and near the asymptotic limit,
RBeH2 ¼ 4:5a0 , show that the wave function is dominated
by a single configuration at either limit. It is also evident
that there is a significant change in the wave function
character, and the graph density at RBeH2 ¼ 2:5a0 displays
the mixed nature of the wave function. The graph density
Reprinted from the journal
-15.4
1
1 A1
1
2 A1
-15.5
E (Eh)
-15.6
-15.7
-15.8
0 1 2 3 4 5 6 7
R Be-H (a )
2 0
Fig. 3 Potential energy surfaces for the 11 A1 and 21 A1 states of
BeH2 along the C2v insertion path. Symbols indicate the MFGCF
results (NGCF ¼ 2 and fmax ¼ 4) and lines denote the CASSCF
energies
plots for the excited state show a more complicated
structure. Near the collinear geometry the open-shell con-
figuration 1a21 2a1 3a1 1b22 dominates; however, for
RBeH2  1:5a0 , the closed-shell configuration 1a21 2a21 3a21
becomes important. The graph densities for the 11 A1 and
21 A1 electronic states are essentially identical near the
transition state geometry at RBeH2 ¼ 2:5a0 . This is
because both states are dominated by the same closed-shell
configurations with nearly identical coefficient magnitudes
at that geometry (Table 1). After the avoided crossing
between the two closed-shell configurations, the 1a21 2a21 1b22
configuration is prominent in the 21 A1 state until
RBeH2  4:0a0 . For longer RBeH2 , the wave function
character is dominated by the open-shell configuration
1a21 2a21 3a1 4a1 , which corresponds to the Beð1 PÞ and
 
H2 R þ g dissociation fragments.
3.2 C2 potential energy surface
The carbon dimer has received considerable attention due
to its importance in interstellar chemistry and combustion
processes [54]. From a theoretical point of view, the car-
bon dimer is interesting because of its unusual bonding, its
complicated electronic structure even near the equilibrium
geometry, and the presence of several low-lying excited
states [55–59]. To assess the robustness of the state-aver-
aged MFGCF approach, the PESs for the three lowest
energy singlet electronic states of C2 were calculated on
the interval 1:5a0  RCC  6:0a0 , where RCC is the distance
between the two carbon atoms. State-averaged CASSCF
13 123
 Theor Chem Acc (2014) 133:1512

2 1 A1 RBe−H2 =0.0a0 2 1 A1 RBe−H2 =2.5a0 2 1 A1 RBe−H2 =4.5a0

b= 0 1 0 2 1 0 b= 0 1 0 2 1 0 b= 0 1 0 2 1 0
2b 2 2b 2 2b 2

1b 2 1b 2 1b 2

1b 1 1b 1 1b 1
level

level

level
4a 1 4a 1 4a 1

3a 1 3a 1 3a 1

2a 1 2a 1 2a 1

0 0 0
b= 0 1 0 2 1 0 b= 0 1 0 2 1 0 b= 0 1 0 2 1 0
2 1 0 2 1 0 2 1 0
a a a

1 1 A1 RBe−H2 =0.0a0 1 1 A1 RBe−H2 =2.5a0 1 1 A1 RBe−H2 =4.5a0

b= 0 1 0 2 1 0 b= 0 1 0 2 1 0 b= 0 1 0 2 1 0
2b 2 2b 2 2b 2

1b 2 1b 2 1b 2

1b 1 1b 1 1b 1
level

level

level
4a 1 4a 1 4a 1

3a 1 3a 1 3a 1

2a 1 2a 1 2a 1

0 0 0
b= 0 1 0 2 1 0 b= 0 1 0 2 1 0 b= 0 1 0 2 1 0
2 1 0 2 1 0 2 1 0
=+1.000E+00
a a a

Fig. 4 Graph density plots for the 11 A1 and 21 A1 states of BeH2 along the C2v insertion reaction path. RBeH2 is defined as the distance between
Be and H2 . Graph densities are computed from an MFGCF wave function with NGCF ¼ 2 and fmax ¼ 4

Table 1 BeH2 coefficients

Configuration RBeH2 ¼ 0:0a0 RBeH2 ¼ 2:5a0 RBeH2 ¼ 4:5a0

11 A1 21 A1 11 A1 21 A1 11 A1 21 A1

1a21 2a21 3a21 0.001 -0.000 -0.633 0.666 -0.947 0.024

1a21 2a21 1b22 0.985 -0.000 0.727 0.647 0.186 -0.184
1a21 2a1 3a1 1b22 0.000 0.974 0.004 -0.044 -0.021 0.010
1a21 2a21 3a1 4a1 0.000 -0.153 0.031 -0.047 -0.087 -0.960

Coefficients of the two dominant closed-shell and the two open-shell configurations in the 11 A1 and 21 A1 electronic states of BeH2 at selected
RBeH2 . The coefficients are extracted from the NGCF ¼ 2 and fmax ¼ 4 MFGCF wave function. 0.000 indicates a small negative number

calculations with equal weights for the three lowest energy
1 the accuracy of the MFGCF wave function as the maxi-
Ag states were used to optimize the core 1rg and 1ru and
the (2  3rg , 1pu;x , 1pu;y , 2  3ru , 1pg;x , 1pg;y Þ active
orbitals within the cc-pVTZ basis set [51]. Natural orbital
resolution is imposed on the active orbital space. State-
averaged full-valence MFGCF calculations with equal
weights for all states are performed with NGCF ¼ 3, and the
convergence of the MFGCF wave function is examined
through a series of calculations with 2  fmax  5. The
lowest energy 1rg and 1ru orbitals are frozen in all
MFGCF calculations. Although dynamic correlation is
neglected, previous work has demonstrated that a full-
valence CASSCF approach captures the important quali-
tative features of the PESs for the three states considered
here [57].
In terms of the nonparallelity error (NPE), Fig. 5 shows
mum number of facets per node is systematically increased.
The NPE is defined as the difference between the maxi-
mum and minimum deviations of the MFGCF energy rel-
ative to the state-averaged CASSCF results. For the three
lowest energy singlet states, the CASSCF results are
reproduced with mEh accuracy for fmax ¼ 3, and the NPE is
\10 lEh for fmax ¼ 5. For all computed PESs, the maxi-
mum errors occur in the region 3:0a0  RCC  4:5a0 and
are at least an order of magnitude larger than the minimum
errors that occur near the dissociation region. This is in
accord with the general observations from earlier studies
[32] using the MFGCF method. The results for the B1 Dg
state are consistently more accurate than those for the 1 Rþ
g

123 14 Reprinted from the journal

Theor Chem Acc (2014) 133:1512

-2 -75.1
10 1 +
X Σg
1
B Δg
1 +
10
-3 B’ Σg
-75.3

E (Eh)
NPE (Eh)

-4
10

1 +
X Σg -75.5
1
10
-5 B Δg
1 +
B’ Σg
average
-6 -75.7
10 2 2 3 4 5 6
3 4 5
R CC (a0)
fmax
Fig. 5 The nonparallelity error in the MFGCF PESs for C2 with Fig. 6 Potential energy surfaces for the X1 Rþ 01 þ 1
g , B Rg , and B Dg
NGCF ¼ 3 and 2  fmax  5 states of C2 . Symbols indicate the MFGCF results (NGCF ¼ 3 and
fmax ¼ 5) and lines denote the CASSCF energies
states. Although the decrease in the NPE between fmax ¼ 4
and 5 for the B01 Rþg state is smaller than expected, the NPE the restricted Hartree–Fock (RHF) configuration
for the state-averaged energy follows the typical trend. 2r2g 2r2u 1p2u;x 1p2u;y (coefficient of 0.84), the coefficient of the
Based on this, we believe that the unexpected shape of the doubly excited configuration 2r2g 1p2u;x 1p2u;y 3r2g in the
NPE for the B01 Rþ g state is not likely to be the result of the MFGCF wave function for the X1 Rþ g state is 0.39. Such a
optimization being trapped in a local minimum, but rather,
large coefficient for a molecule near its equilibrium
it is a consequence of the state-averaged approach for
geometry is rather unusual. Although the coefficient mag-
computing excited-state energies.
nitudes of the two doubly excited configurations
The PESs obtained from the MFGCF wave function
2r2g 2r2u 1p2u;x 3r2g and 2r2g 2r2u 1p2u;y 3r2g are negligible in the
with fmax ¼ 5 are shown in Fig. 6. For short bond distances,
the B01 Rþ 1 X1 Rþ
g wave function, these configurations account for
g state is lower in energy than the B Dg state;
however, by RCC ¼ 2:25a0 , the energies of the two states almost 80 % of the character of the B01 Rþ
g wave function.

switch. By RCC ¼ 3:25a0 , the energy of the B1 Dg state is
below the energy of the X1 Rþ g state. It is also at this point
that the qualitative features of the PESs for the two 1 Rþ
g
states start to display unusual features. As a result of an
avoided crossing, the energy of the X1 Rþg state flattens out
while the PES of the B01 Rþ
g state starts to increase more
steeply. As reported by Boschen et al. [59], this avoided
crossing results in a relatively inaccurate even-tempered
Gaussian fit to the PES. For RCC [ 5:5a0 , the X1 Rþ g state,
in these state-averaged calculations, is once again below
the B1 Dg state, and all three states dissociate to the ground-
state Cð3 PÞ fragments.
The complicated electronic structure of the X1 Rþ g and
B01 Rþg states at selected bond lengths in terms of graph
densities is shown in Fig. 7. Contrary to the BeH2 system
where the ground-state wave function is dominated by a
single configuration near the collinear equilibrium geome-
try, there are several configurations that are important in
describing the X1 Rþ g state at RCC ¼ 2:25a0 . In addition to
The difference in the character of the 1 Rþg states is clearly
reflected by the wider distribution of significant node den-
sities for the B01 Rþ
g state. For RCC  3:25a0 , the appearance
of the graph densities of the two 1 Rþ g states reverse, indi-
cating the drastic change in the wave function character
associated with the avoided crossing. Also note that for both
states, the densities for nodes with b 6¼ 0 or 2 are negligible
near the equilibrium bond distance, and the increased
magnitude of these node densities for RCC ¼ 6:0a0 indicate
the open-shell fragments are near the dissociation limit. At
the RCC ¼ 3:50a0 and RCC ¼ 6:0a0 geometries, the coeffi-
cient in the X1 Rþ 2 2 2 2
g state of the 2rg 2ru 1pu;x 1pu;y configura-
tion, which is dominant at RCC ¼ 2:25a0 , is 0.29 and 0.19,
respectively. This small contribution is evident from the
small (4,0,1) node density in Fig. 7. Single reference
methods have difficulty describing accurately this ground-
state dissociation because of this drastic change in the
nature of the wave function.
For the B1 Dg state, symmetry requires that the coeffi-
cient of the 2r2g 2r2u 1p2u;x 1p2u;y configuration be zero. The

Reprinted from the journal 15 123

 Theor Chem Acc (2014) 133:1512

B’ 1 Σ+
g RCC =2.25a0 B’ 1 Σ+
g RCC =3.50a0 B’ 1 Σ+
g RCC =6.00a0
b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0 b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0 b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0
3σu 3σu 3σu

3σg 3σg 3σg

1πg,y 1πg,y 1πg,y

1πu,y 1πu,y 1πu,y

level

level

level
1πg,x 1πg,x 1πg,x

1πu,x 1πu,x 1πu,x

2σu 2σu 2σu

2σg 2σg 2σg

0 0 0
b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0 b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0 b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0
4 3 2 1 0 4 3 2 1 0 4 3 2 1 0
a a a

X 1 Σ+
g RCC =2.25a0 X 1 Σ+
g RCC =3.50a0 X 1 Σ+
g RCC =6.00a0
b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0 b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0 b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0
3σu 3σu 3σu

3σg 3σg 3σg

1πg,y 1πg,y 1πg,y

1πu,y 1πu,y 1πu,y

level

level

level
1πg,x 1πg,x 1πg,x

1πu,x 1πu,x 1πu,x

2σu 2σu 2σu

2σg 2σg 2σg

0 0 0
b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0 b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0 b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0
4 3 2 1 0 4 3 2 1 0 4 3 2 1 0
=+1.000E+00
a a a

Fig. 7 Graph density plots for the X1 Rþ 01 þ

g and B Rg states of C2 at RCC ¼ 2:25a0 , 3:50a0 , and 6:0a0 . Graph densities are computed from an
MFGCF wave function with NGCF ¼ 3 and fmax ¼ 5

vanishing densities of nodes ð4; 0; 0Þ and ð4; 0; 1Þ in the 3σu

b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0

graph density of the B1 Dg state at RCC ¼ 2:25a0 shown in

3σg
Fig. 8 are consistent with this restriction. Although the
difference in character of the B1 Dg and X1 Rþ g states is
1πg,y

apparent by inspection, this difference is less obvious upon 1πu,y

comparing the density plot of the B1 Dg state to that of the

level

1πg,x
B01 Rþ 2 2 2
g state since, at this geometry, the 2rg 2ru 1pu;x 1pu;y
2
1πu,x
configuration is negligible in both states. Indeed, distin-
2σu
guishing these two states requires the inspection of the
2σg
coefficients for the 2r2g 2r2u 1p2u;x 3r2g and 2r2g 2r2u 1p2u;y 3r2g
configurations in the MFGCF wave function. Within both 0
b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0
states, the magnitude of the coefficients should be the 4 3 2 1 0
same; however, the signs should be the same for the 1 Rþ =+1.000E+00 a
g
states and opposite for the B1 Dg state. In addition to Fig. 8 Graph density plot for the B1 Dg state of C2 at RCC ¼ 2:25a0 .
affording the identification of states with different sym- The graph density is computed from an MFGCF wave function with
metries, these coefficients can also serve as a measure of NGCF ¼ 3 and fmax ¼ 5
the symmetry contamination in the approximate MFGCF
wave function. The magnitude of the symmetry error
surprisingly, these bond distances correspond to points
defined by 2ðjc1 j  jc2 jÞ=ðjc1 j þ jc2 jÞ, where c1 and c2 are
along the PESs where the energies of the two states cross.
the coefficients of the aforementioned configurations, does
not exceed 103 for the entire B01 Rþ g PES. Although the 3.3 H8 model system
symmetry errors for the X1 Rþ 1
g and B Dg states remain
below this threshold for most of the PESs, the symmetry The H8 model of Jankowski et al. [60] consists of four
errors peak near RCC ¼ 3:25a0 and 5:75a0 . Not too interacting stretched H2 molecules arranged in an

123 16 Reprinted from the journal

Theor Chem Acc (2014) 133:1512

elongated octagon. All four molecular bond distances are At a ¼ 0:0001a0 the densities of nodes ð4; 0; 0Þ and
fixed at 2:0a0 . Symmetric displacement of exactly two H2 ð3; 0; 1Þ are approximately equal showing the two-config-
molecules from opposite sides distorts the limiting D8h uration character. At a ¼ 0:1a0 density has shifted from
regular octagonal configuration into various D2h elongated ð3; 0; 1Þ to ð4; 0; 0Þ, and at a ¼ 1:0a0 the density at ð4; 0; 0Þ
octagonal configurations. The model parameter a measures is approaching unity indicating the single-configuration
the displacement as shown in Fig. 9. This system has been character. Thus, the progression of node densities in the
used extensively for benchmarking multireference coupled-
cluster methods [61–64]. The minimal basis set (MBS) of
Huzinaga [65] is employed in most studies and is used α = 1.0 a 0
herein. Investigations performed with double zeta and 2b 1g
b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0

double zeta plus polarization basis sets have concluded that

2b 2u
the MBS model captures all the essential features [66].
For the range 0\a  1:0a0 the eight molecular orbitals 2b 3u

(MOs) in ascending energy order are 1a1g ; 1b2u ; 1b3u ; 1b 1g

2a1g ; 1b1g ; 2b3u ; 2b2u ; and 2b1g . Throughout this range the

level
2a 1g
1
A1g ground-state RHF wave function is 1a21g 1b22u 1b23u 2a21g . 1b 3u
This configuration dominates in the exact wave function 1b 2u
for 0:1a0  a; its coefficient is 0.83 at a ¼ 0:1a0 and 0.94 at
1a 1g
a ¼ 1:0a0 . However, as a approaches 0 the 1b2u and 1b3u
0
MOs approach degeneracy, the highest occupied MO b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0
(HOMO) 2a1g and the lowest unoccupied MO (LUMO) 4 3 2 1 0

1b1g become increasingly quasidegenerate, and the con- a

figuration with a double excitation from the HOMO to the α = 0.1 a 0
LUMO 1a21g 1b22u 1b23u 1b21g becomes increasingly important. 2b 1g
b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0

The exact wave function is predominantly a two-configu- 2b 2u

ration wave function at a ¼ 0 with coefficients of magni-
2b 3u
tude 0.67 and opposite signs for 1a21g 1b22u 1b23u 2a21g and
1b 1g
1a21g 1b22u 1b23u 1b21g .
level

2a 1g
Figure 10 contains a sequence of graph density plots
1b 3u
computed from MFGCF expansions that have been con-
verged to the full-CI limit. The order of levels in these 1b 2u

Shavitt graphs is the same as the MO order above. Of 1a 1g

particular interest are the node densities at the 2a1g level. 0
b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0
4 3 2 1 0
a
3 4
α = 0.0001 a 0
b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0
2b 1g
2 5
2b 2u

2b 3u
α α
1b 1g
level

1 6 2a 1g

1b 3u

1b 2u
8 7
RHH 1a 1g

0
Fig. 9 The H8 model nuclear configurations and parameter defini- b= 0 1 0 2 1 0 3 2 1 0 4 3 2 1 0
tions. All four H2 molecular bond distances RHH are fixed at 2:0a0 . a 4 3 2 1 0
is the displacement from a regular octagon to an elongated octagon of =+1.000E+00 a
D2h symmetry. The drawing is to scale for a equal to 1:0a0 . In the
extended H8 model, all four H2 fragments are displaced symmetri- Fig. 10 Graph density plots for the ground state of the H8 model at
cally from the center of mass along the D4h dissociation path a ¼ 0:0001; 0:1, and 1:0a0

Reprinted from the journal 17 123

 Theor Chem Acc (2014) 133:1512

α(0.1) − α(0.0001) α(0.1) − α(1.0)

b=0 1 0 2 1 0 3 2 1 0 4 3 2 1 0 b=0 1 0 2 1 0 3 2 1 0 4 3 2 1 0
2b1g 2b1g

2b2u 2b2u

2b3u 2b3u

1b1g 1b1g
level

level
2a1g 2a1g

1b3u 1b3u

1b2u 1b2u

1a1g 1a1g

0 0
b=0 1 0 2 1 0 3 2 1 0 4 3 2 1 0 b=0 1 0 2 1 0 3 2 1 0 4 3 2 1 0
4 3 2 1 0 4 3 2 1 0
=+2.500E-01 a a

Fig. 11 Graph density difference plots for the ground state of the H8 model with respect to the a ¼ 0:1a0 geometry. Positive density differences
are green and negative density differences are red

figure reveals the fundamental change in the character of b= 0 1 0

the wave function. The graph density difference plots in

2
Fig. 11 highlight the shift in density. In the left-hand plot
the a ¼ 0:0001a0 density is subtracted from the a ¼ 0:1a0
density, and in the right-hand plot the a ¼ 1:0a0 density is
subtracted from the a ¼ 0:1a0 density. Significant positive
level

density differences are indicated in green, significant neg-
ative density differences are indicated in red, and small
differences of any sign are gray. The sum of the density
differences at any level equals zero. Thus, relatively greater
density for a ¼ 0:1a0 is green in both plots. The left-hand
plot shows density shifting to node ð3; 0; 1Þ in the a ¼
0:0001a0 wave function relative to the a ¼ 0:1a0 wave
function which indicates an increasing contribution of the
1a21g 1b22u 1b23u 1b21g configuration. In contrast, the right-hand
plot shows density shifting to node ð4; 0; 0Þ in the a ¼
1:0a0 wave function relative to the a ¼ 0:1a0 wave func-
tion which indicates an increasing contribution of the
1a21g 1b22u 1b23u 2a21g configuration.
3.4 Extended H8 model system
A straightforward extension of the H8 model of Jankowski
et al. [60] (see Sect. 3.3) is displacement of all four H2
molecules [64]. In particular to study size extensivity, all
H2 molecules are symmetrically displaced to infinity or as a
practical matter in this work to the D4h dissociation
geometry of a ¼ 994a0 . A C1 localized orbital (LO) set
computed from the symmetrically orthonormalized atomic
orbitals [18] is employed. This set corresponds to the
orthonormal MOs that are closest in the least squares sense
to the atomic orbitals. Thus, these molecular calculations
are performed without a preliminary SCF or MCSCF
orbital optimization step. The order of levels in the Shavitt
1
0
b= 0 1 0
=+1.000E+00 1 0
a
Fig. 12 Graph density plot for the ground state of a single H2 in the
extended H8 model using a localized orbital basis
graph is such that the LOs in each H2 are adjacent. Given
these conditions—noninteracting singlet fragments, a LO
basis set, and a fragment ordered Shavitt graph—a single
facet single GCF is formally size extensive. Figure 12
shows the graph density plot computed from a GCF
expansion with NGCF ¼ 1 and fmax ¼ 1 for the ground state
of one H2 in its LO set, and Fig. 13 contains the corre-
sponding plot from an analogous GCF expansion for the
ground state of H8 in this extended model with its LO set
and noninteracting H2 molecules. The H8 plot is clearly
composed of four H2 plots joined head to tail demon-
strating the product nature of the wave function, the gray
nodes in Fig. 13 have zero density verifying that the H2
fragments are noninteracting, and for these GCF expan-
sions the energy of the composite system H8 is
4:411215155407Eh exactly four times that of the frag-
ment H2 energy calculated at 1:102803788852Eh .

123 18 Reprinted from the journal

Theor Chem Acc (2014) 133:1512
b= 0 1 0 2 1 0 3 2 1 0 4 3 2
8
7 molecule fragments are noninteracting, the product struc-
6 ture of the wave function in terms of fragment wave
5
level
4
3 small enough so that the more detailed analyses of the
2 wave functions in terms of CSF coefficients are tractable.
1
0 analyses based on CSF coefficients. Nonetheless, it should
b= 0 1 0 2 1 0 3 2 1 0 4 3 2
4 3 2 1
=+1.000E+00 a sufficient for a detailed analysis of a wave function. Since
Fig. 13 Graph density plot for the ground state of H8 in the extended
model using a localized orbital basis and where the H2 molecules are
well separated and thus noninteracting
4 Conclusion
Among the goals of electronic structure theory are the
prediction of energies of reactions, relative energies of
conformers, and energies of electronic states, as well as
other molecular properties. As a result of the instanta-
neous repulsion between electrons, accurate predictions
demand a complicated wave function structure that often
obfuscates an equally important aspect of electronic
structure theory to provide qualitative chemical insight
into bonding and potential energy surface features. The
MFGCF method allows for both goals to be addressed
simultaneously.
The MFGCF method, in addition to offering the pos-
sibility of reducing the exponential scaling of the exact
wave function with system size, also affords the efficient
manipulation and analysis of the wave function. Although
the MFGCF wave function has a quite complicated
recursive structure, the underlying Shavitt graph coupled
with the graph density concept provides an intuitive
approach for analyzing the character of the wave function.
Since graph densities retain important information related
to the spin-coupling structure of the wave function, they
complement existing analysis methods based on the
density matrix or Mulliken and Löwdin populations. Even
though this concept may be employed with traditional
wave function methods, it is particularly useful in the
context of the MFGCF wave function as the recursive
construction of the graph densities scales polynomially
with system size.
In this work, the MFGCF method was applied to model
systems for studying the changes in wave function char-
acter from a graph density perspective. The graphical
nature of the analysis allows a very intuitive avenue for
Reprinted from the journal
1 0 visualizing the complex changes in the electronic structure.
To wit, for the extended H8 model, in which the four H2
functions is readily apparent and demonstrates the correct
behavior of the MFGCF wave function with system size.
For the systems studied, the sizes of the wave functions are
The qualitative features inferred from the node and arc
densities are in good agreement with the quantitative
1 0
0 be recognized that the graph density concept is not always
the graph density is formally based on the magnitude of the
CSF coefficients, potentially important phase information
is lost. Near avoided crossings, such as in the BeH2 system
examined herein, two states may have nearly indistin-
guishable graph densities. To distinguish the X1 Rþ g and
B01 Rþ 1
g states of C2 from the B Dg states also requires a
more quantitative analysis of the wave function. In both
these cases, the actual CSF coefficients (including sign) are
needed. For larger systems, should the use of CSF or Slater
determinant coefficients be desirable, efficient routines for
extracting the coefficients of user-specified CSFs or Slater
determinants have been developed [32, 37].
The concept of graph density is not only a comple-
mentary wave function analysis tool, but also offers
possibilities for improving the optimization of the
MFGCF wave function parameters. In the current
approach, the number of facets for the individual nodes is
restricted to not exceed some user-specified value fmax .
Clearly, this is not the optimal approach as nodes that
contribute significantly to the wave function or that have
a more multiconfigurational nature may require more
facets than other nodes in order to achieve a specified
wave function accuracy. A method for identifying these
nodes during the optimization is needed. Algorithms
similar to the decimation procedure in density matrix
renormalization group methods [48–50] or concepts rela-
ted to node densities, namely natural facet densities, may
be used to develop reliable tools for identifying these
important nodes. Developments along these lines and the
implementation of an optimization method with dynamic
facet counts will be explored in future work.
Acknowledgments This work was supported by the Office of Basic
Energy Sciences, Division of Chemical Sciences, Geosciences, and
Biosciences, U.S. Department of Energy, under contract DE-AC02-
06CH11357. G.G. was supported by an award from the Research
Corporation for Science Advancement and a grant to Gonzaga Uni-
versity from the Howard Hughes Medical Institute through the
Undergraduate Science Education Program. S.R.B. acknowledges the
use of computational facilities at the Ohio Supercomputer Center.
19 123

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20 Reprinted from the journal
Theor Chem Acc (2014) 133:1522
DOI 10.1007/s00214-014-1522-5
REGULAR ARTICLE
Aspects of size extensivity in unitary group adapted multi-
reference coupled cluster theories: the role of cumulant
decomposition of spin-free reduced density matrices
Rahul Maitra • Debalina Sinha • Sangita Sen •
Debashis Mukherjee
Received: 9 February 2014 / Accepted: 14 June 2014 / Published online: 11 July 2014
 Springer-Verlag Berlin Heidelberg 2014
Abstract We present in this paper a comprehensive study of
the various aspects of size extensivity of a set of unitary group
adapted multi-reference coupled cluster (UGA-MRCC) theo-
ries recently developed by us. All these theories utilize a Jez-
iorski–Monkhorst (JM) inspired spin-free cluster Ansatz of the
P
form jWi ¼ l Xl j/l icl with Xl ¼ fexpðTl Þg, where Tl is
expressed in terms of spin-free generators of the unitary group
UðnÞ for n-orbitals with the associated cluster amplitudes. f:::g
indicates normal ordering with respect to the common closed
shell core part, j0i, of the model functions, f/l g which is taken
as the vacuum. We argue and emphasize in the paper that
maintaining size extensivity of the associated theories is con-
sequent upon (a) connectivity of the composites, Gl , con-
taining the Hamiltonian H and the various powers of T
connected to it, (b) proving the connectivity of the MRCC
equations which involve not only Gl s but also the associated
connected components of the spin-free reduced density
matrices (RDMs) obtained via their cumulant decomposition
and (c) showing the extensivity of the cluster amplitudes for
Rahul Maitra and Debalina Sinha have contributed equally to this
work.
Dedicated to the memory of Professor Isaiah Shavitt and published as
part of the special collection of articles celebrating his many
contributions.
R. Maitra  D. Sinha  S. Sen  D. Mukherjee (&)
Raman Center for Atomic, Molecular and Optical Sciences,
Indian Association for the Cultivation of Science,
Kolkata 700 032, India
e-mail: pcdm@iacs.res.in
Present Address:
R. Maitra
Frick Chemistry Laboratory, Department of Chemistry,
Princeton University, Princeton, NJ 08544, USA
Reprinted from the journal
non-interacting groups of orbitals and eventually of the size-
consistency of the theories in the fragmentation limits. While
we will discuss the aspect (a) above rather briefly, since this
was amply covered in our earlier papers, the aspect (b) and (c),
not covered in detail hitherto, will be covered extensively in
this paper. The UGA-MRCC theories dealt with in this paper
are the spin-free analogs of the state-specific and state-uni-
versal MRCC developed and applied by us recently.We will
explain the unfolding of the proof of extensivity by analyzing
the algebraic structure of the working equations, decomposed
into two factors, one containing the composite Gl that is
connected with the products of cumulants arising out of the
cumulant decomposition of the RDMs and the second term
containing some RDMs which is disconnected from the first
and can be factored out and removed. This factorization ulti-
mately leads to a set of connected MRCC equations. Estab-
lishing the extensivity and size-consistency of the theories
requires careful separation of truly extensive cumulants from
the ones which are a measure of spin correlation and are thus
connected but not extensive. We have discussed in detail, using
diagrams, the factorization procedure and have used suitable
example diagrams to amplify the meanings of the various
algebraic quantities of any diagram. We conclude the paper by
summarizing our findings and commenting on further devel-
opments in the future.
Keywords Unitary group adaptation  Size-extensive SS
and SU MRCC  Spin-free RDM  Spin-free cumulants 
Connectivity of cumulants  Spin correlation of cumulants
1 Introduction
Since a non-relativistic Hamiltonian, H, for the many-
electron problem is spin-free, it’s eigenstates are all
21 123

characterized by fixed eigenvalues for the operator S2 . This
is why it is conceptually and computationally convenient to
describe approximate eigenstates of H as a combination of
basis which are anti-symmetric functions with a fixed
eigenvalue of S2 . There is an enormous literature describ-
ing the various spin-adaptation procedures for a many-
electron function. Among them, three methods, all group
theoretic in origin but using different groups, stand out as:
(a) permutation group (b) SU2 group and (c) unitary group.
Approaches based on these groups have been studied
extensively in the context of electron correlation problems,
in particular for configuration interaction (CI)-based for-
malisms. In spinorbital-based formalisms, the permutation
group [1–7] or SU2 [8] group adaptations fit in naturally in
a CI framework which requires spin adaptation of the CI
coefficients appearing in a linear manner in the wave
function. Both these approaches have found wide use. It is
rather difficult, however, to extend these spin adaptations
to a many-body formalism in a spinorbital basis using
nonlinear cluster Ansatz of the wave operator such as
expðTÞ. Even though spin adaptation can be achieved by
using proper coupling coefficients for the operators T, their
powers still lead to spin contamination. The Unitary Group
Approach (UGA), on the other hand, has the property that a
spin-free operator can be written in terms of spin-free
generators of the unitary group whose powers also remain
spin free. Hence, a coupled cluster representation of the
wave operator for a spin-free T is spin free. For developing
spin-free many-body theories, a unitary group approach
(UGA) is thus the most natural choice. We may mention
here that a UGA path to other nonlinear Ansätze for a wave
function has also been explored in recent years [9–12].
From now on, we will refer to the spin-free generators of
the unitary group as generators.
The application of unitary group to nuclear many-fer-
mion problem involving Hamiltonians which are spin and
iso-spin independent was developed by Moshinsky and
Seligman [13–15]. The spin-free formulation for the spin-
independent many-electron Hamiltonian was considered
earlier by Matsen [16, 17]. But it is only after the advent of
group theoretic simplifications for a Hamiltonian which is
spin independent (and having no additional quantum
number like iso-spin) via a unitary group approach by
Paldus [18], the concomitant graphical representation by
Shavitt [19, 20] of the unitary group adapted spatial
Gel’fand states and of the associated matrix elements of
generators between two Gel’fand states that the true rev-
olution in compact and efficient unitary group-based spin-
free theories was achieved. Subsequently, more efficient
and general formulae for matrix element evaluation were
developed, comprehensive accounts of which can be found
in Refs. [21, 22]. The advantages of the unitary group
123
Theor Chem Acc (2014) 133:1522
formulation lie in the efficient evaluation of the possible
matrix elements involving generators for which, at the
current stage of development of quantum chemistry, there
are already very efficient computer codes [23–29] which
any new many-electron theory can embed in its own code
for its own unitary spin-adaptation strategy. UGA theories
have been utilized for CI [23], MCSCF [30–32] and spin-
free single CSF-based UGA CC [33, 34]. There was also a
prescient proposal for UGA-SUMRCC [33] using the
Jeziorski–Monkhorst (JM)-type multi-exponential Ansatz.
It is important to mention here that for any practical
implementation of a UGA scheme, one need not demand
that the n-electron CSF’s be adapted to UðnÞ. Rather, it is
expedient to demand that the CSF’s be adapted to the
subgroup of UðnÞ; uðnÞ ¼ Uðnc Þ  Uðna Þ  Uðnv Þ, where
nc , na , and nv are, respectively, the number of core, active,
and virtual orbitals. This is simply due to the physical
requirement that the maximum invariance of an approxi-
mate function that one may practically impose is the
invariance of the function and the energy with respect to
separate unitary transformation among core, active, and
virtual orbitals. This was indeed done in the UGA CC
papers by Paldus and others [33, 34]. In particular, both
these papers have used the uðnÞ-adapted scalar tensor
generators in their choice of excitation operators. We also
point out two references [35, 36] in this context where
useful discussions of other UGA-based approaches and
their interrelation can be found. Reference [36] has also
presented in considerable detail a number of approximately
spin-adapted CC approaches and their relationship with
UGA CC. We also point out that Li and Paldus have
applied the UGA CC method to many problems (see e.g.,
Refs. 39–48 in [37]).
As emphasized in the first para of our introduction, a
spin-adapted formulation of any coupled cluster formalism
using spinorbital basis is beset by the problem of spin
contamination of the function for terms containing non-
linear powers of the cluster operators acting on the refer-
ence function. Nevertheless, progress was made in the
development of such spin adapted formalisms by imposing
on the wave function the constraint that the final function
be an eigen function of the total spin with a fixed eigen-
value [38, 39]. An approximate spin-adapted formulation
where the expectation value of S2 is constrained to a fixed
value corresponding to a given spin was considered
somewhat earlier [40]. Nooijen and Bartlett have proposed
a unitary group-based spin-adapted open-shell coupled
cluster for a single reference function [41]. We should also
mention the spin-adapted cluster (SAC) expansion for-
malism of Nakatsuji [42, 43] in this context. Here also, the
linear term of the cluster expansion of the wave function is
spin adapted although the full wave function is not.
22 Reprinted from the journal
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 Le roi Louis XVIII était remonté sur le trône; tout espoir de rester
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bas du conte de Micromégas, le roi avait écrit:[2]

«Tranquillise-toi, ma chère Caroline; quoique bien

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partout où j’irai mon cœur sera à toi et à mes enfans.
»J. M.»

Dix minutes après, Murat et son hôte attendaient sur la plage de

Bonette l’arrivée du canot qui devait conduire le fugitif à son
bâtiment.
Ils attendirent ainsi jusqu’à midi, et rien ne parut; et cependant ils
voyaient à l’horizon le brick sauveur qui, ne pouvant tenir l’ancre à
cause de la profondeur de la mer, courait des bordées, au risque,
par cette manœuvre, de donner l’éveil aux sentinelles de la côte. A
midi, le roi, écrasé de fatigue, brûlé par le soleil, était couché sur la
plage, lorsqu’un domestique arriva portant quelques
rafraîchissemens que madame Marouin, inquiète, envoyait à tout
hasard à son mari. Le roi prit un verre d’eau rougie, mangea une
orange, se releva un instant pour regarder si, dans l’immensité de
cette mer, il ne verrait pas venir à lui la barque qu’il attendait. La mer
était déserte, et le brick seul se courbait gracieusement à l’horizon,
impatient de partir comme un cheval qui attend son maître.
Le roi poussa un soupir et se recoucha sur le sable. Le
domestique retourna à Bonette avec l’ordre d’envoyer à la plage le
frère de monsieur Marouin. Un quart d’heure après il arrivait, et
presque aussitôt il repartait à grande course de cheval pour Toulon,
afin de savoir de monsieur Bonafoux la cause qui avait empêché la
barque de venir prendre le roi. En arrivant chez le capitaine, il trouva
la maison envahie par la force armée; on faisait une visite
domiciliaire dont Murat était l’objet. Le messager parvint enfin au
milieu du tumulte jusqu’à celui auprès duquel il était envoyé, et là il
apprit que le canot était parti à l’heure convenue, et qu’il fallait qu’il
se fût égaré dans les calangues de Saint-Louis et de Sainte-
Marguerite. C’est en effet ce qui était arrivé. A cinq heures, monsieur
Marouin rapportait ces nouvelles à son frère et au roi. Elles étaient
embarrassantes. Le roi n’avait plus le courage de défendre sa vie,
même par la fuite; il était dans un de ces momens d’abattement qui
saisissent parfois l’homme le plus fort, incapable d’émettre une
opinion pour sa propre sûreté, et laissant monsieur Marouin maître
d’y pourvoir comme bon lui semblerait. En ce moment un pêcheur
rentrait en chantant dans le port. Marouin lui fit signe de venir, il
obéit.
Marouin commença par acheter à cet homme tout le poisson qu’il
avait pris; puis, après qu’il l’eut payé avec quelques pièces de
monnaie, il fit briller de l’or à ses yeux, et lui offrit trois louis s’il
voulait conduire un passager au brick que l’on apercevait en face de
la Croix-des-Signaux. Le pêcheur accepta. Cette chance de salut
rendit à l’instant même toutes ses forces à Murat; il se leva,
embrassa monsieur Marouin, lui recommanda d’aller trouver sa
femme et de lui remettre le volume de Voltaire, puis il s’élança dans
la barque, qui s’éloigna aussitôt.
Elle était déjà à quelque distance de la côte, lorsque le roi arrêta
le rameur et fit signe à Marouin qu’il avait oublié quelque chose. En
effet, sur la plage était un sac de nuit dans lequel Murat avait
renfermé une magnifique paire de pistolets montés en vermeil, qui
lui avait été donnée par la reine, et à laquelle il tenait
prodigieusement. A peine fut-il à la portée de la voix, qu’il indiqua à
son hôte le motif de son retour. Celui-ci prit aussitôt la valise, et,
sans attendre que Murat touchât terre, il la lui jeta de la plage dans
le bateau; en tombant, le sac de nuit s’ouvrit, et un des pistolets en
sortit. Le pêcheur ne jeta qu’un coup d’œil sur l’arme royale, mais ce
fut assez pour qu’il remarquât sa richesse et qu’il conçût des
soupçons. Il n’en continua pas moins de ramer vers le bâtiment.
Monsieur Marouin, le voyant s’éloigner, laissa son frère sur la côte,
et, saluant une dernière fois le roi, qui lui rendit son salut, retourna
vers la maison pour calmer les inquiétudes de sa femme et prendre
lui-même quelques heures de repos dont il avait grand besoin.
Deux heures après, il fut réveillé par une visite domiciliaire; sa
maison, à son tour, était envahie par la gendarmerie. On chercha de
tous les côtés sans trouver trace du roi. Au moment où les
recherches étaient le plus acharnées, son frère rentra; Marouin le
regarda en souriant, car il croyait le roi sauvé; mais à l’expression du
visage de l’arrivant, il vit qu’il était advenu quelque nouveau malheur.
Aussi, au premier moment de relâche que lui donnèrent les visiteurs,
il s’approcha de son frère:
—Eh bien! dit-il, le roi est à bord, j’espère?
—Le roi est à cinquante pas d’ici, caché dans la masure.
—Pourquoi est-il revenu?
—Le pêcheur a prétexté un gros temps, et a refusé de le
conduire jusqu’au brick.
—Le misérable!
 Les gendarmes rentrèrent.
Toute la nuit se passa en visites infructueuses dans la maison et
ses dépendances; plusieurs fois ceux qui cherchaient le roi
passèrent à quelques pas de lui, et Murat put entendre leurs
menaces et leurs imprécations. Enfin, une demi-heure avant le jour,
ils se retirèrent. Marouin les laissa s’éloigner, et aussitôt qu’il les eut
perdus de vue, il courut à l’endroit où devait être le roi. Il le trouva
couché dans un enfoncement et tenant un pistolet de chaque main.
Le malheureux n’avait pu résister à la fatigue et s’était endormi. Il
hésita un instant à le rendre à cette vie errante et tourmentée; mais il
n’y avait pas une minute à perdre. Il le réveilla.
Aussitôt ils s’acheminèrent vers la côte; le brouillard matinal
s’étendait sur la mer. On ne pouvait distinguer à deux cents pas de
distance: ils furent obligés d’attendre. Enfin les premiers rayons du
soleil commencèrent à attirer à eux cette vapeur nocturne; elle se
déchira, glissant sur la mer, pareille aux nuages qui glissent au ciel.
L’œil avide du roi plongeait dans chacune des vallées humides qui
se creusaient devant lui, sans y rien distinguer; cependant il espérait
toujours que derrière ce rideau mobile il finirait par apercevoir le
brick sauveur. Peu à peu l’horizon s’éclaircit; de légères vapeurs,
semblables à des fumées, coururent encore quelque temps à la
surface de la mer, et dans chacune d’elles le roi croyait reconnaître
les voiles blanches de son vaisseau. Enfin la dernière s’effaça
lentement, la mer se révéla dans toute son immensité; elle était
déserte. Le brick, n’osant attendre plus long-temps, était parti
pendant la nuit.
—Allons, dit le roi en se retournant vers son hôte, le sort en est
jeté, j’irai en Corse.
Le même jour, le maréchal Brune était assassiné à Avignon.
 II.
LA CORSE.

C’est encore sur cette même plage de Bonette, dans cette même
baie où nous l’avons vu attendre inutilement le canot de son brick,
que toujours accompagné de son hôte fidèle, nous allons retrouver
Murat le 22 août de la même année. Ce n’était plus alors par
Napoléon qu’il était menacé, c’est par Louis XVIII qu’il était proscrit:
ce n’était plus la loyauté militaire de Brune qui venait, les larmes aux
yeux, lui signifier les ordres qu’il avait reçus, c’était l’ingratitude
haineuse de monsieur de Rivière, qui mettait à prix[3] la tête de celui
qui avait sauvé la sienne[4]. Monsieur de Rivière avait bien écrit à
l’ex-roi de Naples de s’abandonner à la bonne foi et à l’humanité du
roi de France, mais cette vague invitation n’avait point paru au
proscrit une garantie suffisante, surtout de la part d’un homme qui
venait de laisser égorger, presque sous ses yeux, un maréchal de
France porteur d’un sauf-conduit signé de sa main. Murat savait le
massacre des Mameluks à Marseille, l’assassinat de Brune à
Avignon; il avait été prévenu la veille par le commissaire de police de
Toulon[5] que l’ordre formel avait été donné de l’arrêter: il n’y avait
donc pas moyen de rester plus longtemps en France. La Corse,
avec ses villes hospitalières, ses montagnes amies et ses forêts
impénétrables, était à cinquante lieues à peine; il fallait gagner la
Corse, et attendre dans ses villes, dans ses montagnes ou dans ses
forêts, ce que les rois décideraient relativement au sort de celui
qu’ils avaient appelé sept ans leur frère.
A dix heures du soir, le roi descendit sur la plage. Le bateau qui
devait l’emporter n’était pas encore au rendez-vous; mais, cette fois,
il n’y avait aucune crainte qu’il y manquât; la baie avait été reconnue,
pendant la journée, par trois amis dévoués à la fortune adverse:
c’étaient messieurs Blancard, Langlade et Donadieu, tous trois
officiers de marine, hommes de tête et de cœur, qui s’étaient
engagés sur leur vie à conduire Murat en Corse, et qui en effet
allaient exposer leur vie pour accomplir leur promesse. Murat vit
donc sans inquiétude la plage déserte: ce retard, au contraire, lui
donnait quelques instans de joie filiale. Sur ce bout de terrain, sur
cette langue de sable, le malheureux proscrit se cramponnait encore
à la France, sa mère, tandis qu’une fois le pied posé sur ce bâtiment
qui allait l’emporter, la séparation devait être longue, sinon éternelle.
Au milieu de ces pensées, il tressaillit tout-à-coup et poussa un
soupir: il venait d’apercevoir, dans l’obscurité transparente de la nuit
méridionale, une voile glissant sur les vagues comme un fantôme.
Bientôt un chant de marin se fit entendre; Murat reconnut le signal
convenu, il y répondit en brûlant l’amorce d’un pistolet, et aussitôt la
barque se dirigea vers la terre; mais, comme elle tirait trois pieds
d’eau, elle fut forcée de s’arrêter à dix ou douze pas de la plage;
deux hommes se jetèrent aussitôt à la mer, et gagnèrent le bord, le
troisième resta enveloppé dans son manteau et couché près du
gouvernail.
—Eh bien! mes braves amis, dit le roi en allant au-devant de
Blancard et de Langlade jusqu’à ce qu’il sentît la vague mouiller ses
pieds, le moment est arrivé, n’est-ce pas? Le vent est bon, la mer
calme; il faut partir.
—Oui, répondit Langlade, oui, sire, il faut partir, et peut-être
cependant serait-il plus sage de remettre la chose à demain.
—Pourquoi? reprit Murat.
Langlade ne répondit point; mais, se tournant vers le couchant, il
leva la main, et, selon l’habitude des marins, il siffla pour appeler le
vent.
—C’est inutile, dit Donadieu, qui était resté dans la barque, voici
les premières bouffées qui arrivent, bientôt tu en auras à n’en savoir
que faire... Prends garde, Langlade, prends garde, parfois en
appelant le vent on éveille la tempête.—Murat tressaillit, car il
semblait que cet avis, qui s’élevait de la mer, lui était donné par
l’esprit des eaux; mais l’impression fut courte, et il se remit à
l’instant.
—Tant mieux, dit-il, plus nous aurons de vent, plus vite nous
marcherons.
—Oui, répondit Langlade, seulement Dieu sait où il nous
conduira, s’il continue à tourner ainsi.
—Ne partez pas cette nuit, sire, dit Blancard, joignant son avis à
celui de ses deux compagnons.
—Mais enfin, pourquoi cela?
—Parce que, vous voyez cette ligne noire, n’est-ce pas? eh bien!
au coucher du soleil elle était à peine visible, la voilà maintenant qui
couvre une partie de l’horizon; dans une heure il n’y aura plus une
étoile au ciel.
—Avez-vous peur? dit Murat.
—Peur! répondit Langlade, et de quoi? de l’orage? il haussa les
épaules. C’est à-peu-près comme si je demandais à votre majesté si
elle a peur d’un boulet de canon... Ce que nous en disons, c’est pour
vous, sire; mais que voulez-vous que fasse l’orage à des chiens de
mer comme nous?
—Partons donc! s’écria Murat en poussant un soupir. Adieu,
Marouin... Dieu seul peut vous récompenser de ce que vous avez
fait pour moi. Je suis à vos ordres, messieurs.
A ces mots, les deux marins saisirent le roi chacun par une
cuisse, et l’élevant sur leurs épaules, ils entrèrent aussitôt dans la
mer; en un instant il fut à bord, Langlade et Blancard montèrent
derrière lui, Donadieu resta au gouvernail; les deux autres officiers
se chargèrent de la manœuvre et commencèrent leur service en
déployant les voiles. Aussitôt, comme un cheval qui sent l’éperon, la
petite barque sembla s’animer; les marins jetèrent un coup d’œil
insoucieux vers la terre, et Murat, sentant qu’il s’éloignait, se
retourna du côté de son hôte et lui cria une dernière fois:
 —Vous avez votre itinéraire jusqu’à Trieste. N’oubliez pas ma
femme!... Adieu!... Adieu.
—Dieu vous garde, sire, murmura Marouin.—Et quelque temps
encore, grâce à la voile blanche qui se dessinait dans l’ombre, il put
suivre des yeux la barque qui s’éloignait rapidement; enfin elle
disparut. Marouin resta encore quelque temps sur le rivage, quoiqu’il
ne vît plus rien; alors un cri affaibli par la distance parvint encore
jusqu’à lui: ce cri était le dernier adieu de Murat à la France.
Lorsque monsieur Marouin me raconta un soir, au lieu même où
la chose s’était passée, les détails que je viens de décrire, ils lui
étaient si présens, quoique vingt ans se fussent écoulés depuis lors,
qu’il se rappelait jusqu’aux moindres accidens de cet embarquement
nocturne. De ce moment, il m’assura qu’un pressentiment de
malheur l’avait saisi, qu’il ne pouvait s’arracher de cette plage, et
que plusieurs fois l’envie lui prit de rappeler le roi; mais, pareil à un
homme qui rêve, sa bouche s’ouvrait sans laisser échapper aucun
son. Il craignait de paraître insensé; et ce ne fut qu’à une heure du
matin, c’est-à-dire deux heures et demie après le départ de la
barque, qu’il rentra chez lui avec une tristesse mortelle dans le cœur.
Quant aux aventureux navigateurs, ils s’étaient engagés dans
cette large ornière marine qui mène de Toulon à Bastia, et d’abord
l’événement parut, aux yeux du roi, démentir la prédiction de nos
marins: le vent, au lieu de s’augmenter, tomba peu à peu, et deux
heures après le départ, la barque se balançait sans reculer ni
avancer sur des vagues qui, de minute en minute, allaient
s’aplanissant. Murat regardait tristement s’éteindre, sur cette mer où
il se croyait enchaîné, le sillon phosphorescent que le petit bâtiment
traînait après lui: il avait amassé du courage contre la tempête, mais
non contre le calme; et, sans même interrompre ses compagnons de
voyage, à l’inquiétude desquels il se méprenait, il se coucha au fond
du bateau, s’enveloppa de son manteau, et fermant les yeux comme
s’il dormait, il s’abandonna au flot de ses pensées, bien autrement
tumultueux et agité que celui de la mer. Bientôt les deux marins,
croyant à son sommeil, se réunirent au pilote, et, s’asseyant près du
gouvernail, commencèrent à tenir conseil.
 —Vous avez eu tort, Langlade, dit Donadieu, de prendre une
barque ou si petite ou si grande: sans pont nous ne pouvons résister
à la tempête, et sans rames nous ne pouvons avancer dans le
calme.
—Sur Dieu! je n’avais pas le choix. J’ai été obligé de prendre ce
que j’ai rencontré, et si ce n’était pas l’époque des madragues[6], je
n’aurais pas même trouvé cette mauvaise péniche, ou bien il me
l’aurait fallu aller chercher dans le port, et la surveillance est telle
que j’y serais bien entré, mais que je n’aurais probablement pas pu
en sortir.
—Est-elle solide au moins? dit Blancard.
—Pardieu! tu sais bien ce que c’est que des planches et des
clous qui trempent depuis dix ans dans l’eau salée. Dans les
occasions ordinaires on n’en voudrait pas pour aller de Marseille au
château d’If; dans une circonstance comme la nôtre on ferait le tour
du monde dans une coquille de noix.
—Chut! dit Donadieu. Les marins écoutèrent: un grondement
lointain se fit entendre, mais si faible, qu’il fallait l’oreille exercée d’un
enfant de la mer pour le distinguer.
—Oui, oui, dit Langlade; c’est un avertissement pour ceux qui ont
des jambes ou des ailes de regagner le nid qu’ils n’auraient pas dû
quitter.
—Sommes-nous loin des îles? dit vivement Donadieu.
—A une lieue environ.
—Mettez le cap sur elles.
—Et pour quoi faire? dit Murat en se soulevant.
—Pour y relâcher, sire, si nous le pouvons...
—Non, non! s’écria Murat, je ne veux plus remettre le pied à terre
qu’en Corse; je ne veux pas quitter encore une fois la France.
D’ailleurs, la mer est calme, et voilà le vent qui nous revient...
 —Tout à bas! cria Donadieu.
Aussitôt Langlade et Blancard se précipitèrent pour exécuter la
manœuvre. La voile glissa le long du mât, et s’abattit au fond du
bâtiment.
—Que faites-vous? cria Murat; oubliez-vous que je suis roi et que
j’ordonne?
—Sire, dit Donadieu, il y a un roi plus puissant que vous ici, c’est
Dieu; il y a une voix qui couvre la vôtre, c’est celle de la tempête...
Laissez-nous sauver votre majesté, si la chose est possible, et
n’exigez rien de plus...
En ce moment un éclair sillonna l’horizon, un coup de tonnerre,
plus rapproché que le premier, se fit entendre, une légère écume
monta à la surface de l’eau, la barque frissonna comme un être
animé. Murat commença à comprendre que le danger venait; alors il
se leva en souriant, jeta derrière lui son chapeau, secoua ses longs
cheveux, aspira l’orage comme il aspirait la fumée; le soldat était
prêt à combattre.
—Sire, dit Donadieu, vous avez bien vu des batailles; mais peut-
être n’avez-vous point vu une tempête: si vous êtes curieux de ce
spectacle, cramponnez-vous au mât et regardez, car en voilà une
qui se présente bien.
—Que faut-il que je fasse? dit Murat; ne puis-je vous aider en
rien?
—Non! pas pour le moment, sire; plus tard nous vous
emploierons aux pompes...
Pendant ce dialogue, l’orage avait fait des progrès; il arrivait sur
les voyageurs comme un cheval de course, soufflant le vent et le feu
par ses naseaux, hennissant le tonnerre et faisant voler l’écume des
vagues sous ses pieds. Donadieu pressa le gouvernail, la barque
céda comme si elle comprenait la nécessité d’une prompte
obéissance, et présenta sa poupe au choc du vent; alors la
bourrasque passa laissant derrière elle la mer tremblante, et tout
parut rentrer dans le repos. La tempête reprenait haleine.
—En sommes-nous donc quittes pour cette rafale? dit Murat.
—Non, votre majesté, dit Donadieu, ceci n’est qu’une affaire
d’avant-garde; tout-à-l’heure le corps d’armée va donner.
—Et ne faisons-nous pas quelques préparatifs pour le recevoir?
répondit gaîment le roi.
—Lesquels? dit Donadieu. Nous n’avons plus un pouce de toile
où le vent puisse mordre, et tant que la barque ne fera pas eau nous
flotterons comme un bouchon de liége. Tenez-vous bien, sire!...
En effet, une seconde bourrasque accourait, plus rapide que la
première, accompagnée de pluie et d’éclairs. Donadieu essaya de
répéter la même manœuvre, mais il ne put virer si rapidement que le
vent n’enveloppât la barque; le mât se courba comme un roseau; le
canot embarqua une vague.
—Aux pompes, cria Donadieu! Sire, voilà le moment de nous
aider...
Blancard, Langlade et Murat saisirent leurs chapeaux et se
mirent à vider la barque. La position de ces quatre hommes était
affreuse, elle dura trois heures. Au point du jour le vent faiblit;
cependant la mer resta grosse et tourmentée. Le besoin de manger
commença à se faire sentir; toutes les provisions avaient été
atteintes par l’eau de mer, le vin seul avait été préservé du contact.
Le roi prit une bouteille, en avala le premier quelques gorgées; puis il
la passa à ses compagnons, qui burent à leur tour: la nécessité avait
chassé l’étiquette. Langlade avait par hasard sur lui quelques
tablettes de chocolat, qu’il offrit au roi. Murat en fit quatre parts
égales et força ses compagnons de manger; puis, le repas fini, on
orienta vers la Corse; mais la barque avait tellement souffert qu’il n’y
avait pas probabilité qu’elle pût gagner Bastia.
Le jour se passa tout entier sans que les voyageurs pussent faire
plus de dix lieues; ils naviguaient sous la petite voile; de foque,
n’osant tendre la grande voile, et le vent était si variable, que le
temps se perdait à combattre ses caprices. Le soir une voie d’eau se
déclara; elle pénétrait à travers les planches disjointes; les
mouchoirs réunis de l’équipage suffirent pour tamponner la barque,
et la nuit, qui descendit triste et sombre, les enveloppa pour la
seconde fois de son obscurité. Murat écrasé de fatigue, s’endormit;
Blancard et Langlade reprirent place près de Donadieu; et ces trois
hommes, qui semblaient insensibles au sommeil et à la fatigue,
veillèrent à la tranquillité de son sommeil.
La nuit fut, en apparence, assez tranquille; cependant
quelquefois des craquemens sourds se faisaient entendre. Alors les
trois marins se regardaient avec une expression étrange; puis leurs
yeux se reportaient vers le roi, qui dormait au fond de ce bâtiment,
dans son manteau trempé d’eau de mer, aussi profondément qu’il
avait dormi dans les sables de l’Egypte et dans les neiges de la
Russie. Alors l’un d’eux se levait, s’en allait à l’autre bout du canot
en sifflant entre ses dents l’air d’une chanson provençale... puis,
après avoir consulté le ciel, les vagues et la barque, il revenait
auprès de ses camarades, et se rasseyait en murmurant:—C’est
impossible; à moins d’un miracle, nous n’arriverons jamais.—La nuit
s’écoula dans ces alternatives. Au point du jour on se trouva en vue
d’un bâtiment:—Une voile! s’écria Donadieu, une voile! A ce cri le roi
se réveilla. En effet, un petit brick marchand apparaissait, venant de
Corse et faisant route vers Toulon. Donadieu mit le cap sur lui,
Blancard hissa les voiles au point de fatiguer la barque, et Langlade
courut à la proue, élevant le manteau du roi au bout d’une espèce de
harpon. Bientôt les voyageurs s’aperçurent qu’ils avaient été vus; le
brick manœuvra de manière à se rapprocher d’eux; au bout de dix
minutes ils se trouvèrent à cinquante pas l’un de l’autre. Le capitaine
parut sur l’avant. Alors le roi le héla, lui offrant une forte récompense
s’il voulait le recevoir à bord avec ses trois compagnons et les
conduire en Corse. Le capitaine écouta la proposition; puis aussitôt,
se tournant vers l’équipage, il donna à demi-voix un ordre que
Donadieu ne put entendre, mais qu’il saisit probablement par le
geste, car aussitôt il commanda à Langlade et à Blancard une
manœuvre qui avait pour but de s’éloigner du bâtiment. Ceux-ci
obéirent avec la promptitude passive des marins; mais le roi frappa
du pied:
—Que faites-vous, Donadieu? que faites-vous? s’écria-t-il; ne
voyez-vous pas qu’il vient à nous?
—Oui, sur mon âme! je le vois... Obéissez, Langlade; alerte,
Blancard. Oui, il vient sur nous, et peut-être m’en suis-je aperçu trop
tard. C’est bien, c’est bien; à moi maintenant. Alors il se coucha sur
le gouvernail, et lui imprima un mouvement si subit et si violent, que
la barque, forcée de changer immédiatement de direction, sembla se
raidir contre lui, comme ferait un cheval contre le frein; enfin elle
obéit. Une vague énorme, soulevée par le géant qui venait sur elle,
l’emporta avec elle comme une feuille; le brick passa à quelques
pieds de sa poupe.
—Ah! traître! s’écria le roi, qui commença seulement à
s’apercevoir de l’intention du capitaine; en même temps il tira un
pistolet de sa ceinture, en criant: A l’abordage, à l’abordage! et
essaya de faire feu sur le brick; mais la poudre était mouillée et ne
s’enflamma point. Le roi était furieux, et ne cessait de crier: A
l’abordage, à l’abordage!
—Oui, oui, le misérable, ou plutôt l’imbécile, dit Donadieu, il nous
a pris pour des forbans, et il a voulu nous couler, comme si nous
avions besoin de lui pour cela.
En effet, jetant les yeux sur le canot, il était facile de s’apercevoir
qu’il commençait à faire eau. La tentative de salut que venait de
risquer Donadieu avait effroyablement fatigué la barque, et la mer
entrait par plusieurs écartemens de planches; il fallut se mettre à
puiser l’eau avec les chapeaux; ce travail dura dix heures. Enfin
Donadieu fit, pour la seconde fois, entendre le cri sauveur:—Une
voile! une voile!...
Le roi et ses deux compagnons cessèrent aussitôt leur travail; on
hissa de nouveau les voiles, on mit le cap sur le bâtiment qui
s’avançait et l’on cessa de s’occuper de l’eau, qui, n’étant plus
combattue, gagna rapidement.
 Désormais c’était une question de temps, de minutes, de
secondes, voilà tout; il s’agissait d’arriver au bâtiment avant de
couler bas. Le bâtiment, de son côté, semblait comprendre la
position désespérée de ceux qui imploraient son secours, il venait au
pas de course; Langlade le reconnut le premier, c’était une
balancelle du gouvernement, un bateau de poste qui faisait le
service entre Toulon et Bastia. Langlade était l’ami du capitaine, il
l’appela par son nom avec cette voix puissante de l’agonie, et il fut
entendu. Il était temps, l’eau gagnait toujours; le roi et ses
compagnons étaient déjà dans la mer jusqu’aux genoux; le canot
gémissait comme un mourant qui râle; il n’avançait plus et
commençait à tourner sur lui-même. En ce moment, deux ou trois
câbles, jetés de la balancelle, tombèrent dans la barque; le roi en
saisit un, s’élança et saisit l’échelle de corde: il était sauvé. Blancard
et Langlade en firent autant presque aussitôt; Donadieu resta le
dernier, comme c’était son devoir de le faire, et au moment où il
mettait un pied sur l’échelle du bord, il sentit sous l’autre s’enfoncer
la barque qu’il quittait; il se retourna avec la tranquillité d’un marin,
vit le gouffre ouvrir sa vaste gueule au-dessous de lui, et aussitôt la
barque dévorée tournoya et disparut. Cinq secondes encore, et ces
quatre hommes, qui maintenant étaient sauvés, étaient à tout jamais
perdus!...[7]
Murat était à peine sur le pont, qu’un homme vint se jeter à ses
pieds; c’était un mameluk qu’il avait autrefois ramené d’Egypte, et
qui s’était depuis marié à Castellamare; des affaires de commerce
l’avaient attiré à Marseille, où, par miracle, il avait échappé au
massacre de ses frères; et, malgré le déguisement qui le couvrait et
les fatigues qu’il venait d’essuyer, il avait reconnu son ancien maître.
Ses exclamations de joie ne permirent pas au roi de garder plus
longtemps son incognito; alors le sénateur Casablanca, le capitaine
Oletta, un neveu du prince Baciocchi, un ordonnateur nommé
Boërco, qui fuyaient eux-mêmes les massacres du Midi, se trouvant
sur le bâtiment, le saluèrent du nom de majesté et lui improvisèrent
une petite cour: le passage était brusque, il opéra un changement
rapide; ce n’était plus Murat le proscrit, c’était Joachim Ier, roi de
Naples. La terre de l’exil disparut avec la barque engloutie; à sa
place, Naples et son golfe magnifique apparurent à l’horizon comme
un merveilleux mirage, et sans doute la première idée de la fatale
expédition de Calabre prit naissance pendant ces jours d’enivrement
qui suivirent les heures d’agonie. Cependant le roi, ignorant encore
quel accueil l’attendait en Corse, prit le nom de comte de Campo
Melle, et ce fut sous ce nom que le 25 août il prit terre à Bastia. Mais
sa précaution fut inutile; trois jours après son arrivée, personne
n’ignorait plus sa présence dans cette ville. Des rassemblemens se
formèrent aussitôt, des cris de: Vive Joachim! se firent entendre, et
le roi, craignant de troubler la tranquillité publique, sortit le même
soir de Bastia avec ses trois compagnons et son mameluk. Deux
heures après il entrait à Viscovato, et frappait à la porte du général
Franceschetti, qui avait été à son service tout le temps de son règne,
et qui, ayant quitté Naples en même temps que le roi, était revenu
en Corse habiter avec sa femme la maison de monsieur Colona
Cicaldi, son beau-père. Il était en train de souper lorsqu’on vint lui
dire qu’un étranger demandait à lui parler: il sortit et trouva Murat
enveloppé d’une capote militaire, la tête enfoncée dans un bonnet
de marin, la barbe longue, et portant un pantalon, des guêtres et des
souliers de soldat. Le général s’arrêta étonné; Murat fixa sur lui son
grand œil noir; puis, croisant les bras:—Franceschetti, lui dit-il, avez-
vous à votre table une place pour votre général qui a faim? avez-
vous sous votre toit un asile pour votre roi qui est proscrit?...
Franceschetti jeta un cri de surprise en reconnaissant Joachim, et ne
put lui répondre qu’en tombant à ses pieds et en lui baisant la main.
De ce moment, la maison du général fut à la disposition de Murat.
A peine le bruit de l’arrivée du roi fut-il répandu dans les environs
que l’on vit accourir à Viscovato des officiers de tous grades, des
vétérans qui avaient combattu sous lui, et des chasseurs corses que
son caractère aventureux séduisait; en peu de jours la maison du
général fut transformée en palais, le village en résidence royale, et
l’île en royaume. D’étranges bruits se répandirent sur les intentions
de Murat; une armée de neuf cents hommes contribuait à leur
donner quelque consistance. C’est alors que Blancard, Langlade et
Donadieu prirent congé de lui; Murat voulut les retenir; mais ils
s’étaient voués au salut du proscrit, et non à la fortune du roi.
 Nous avons dit que Murat avait rencontré à bord du bateau de
poste de Bastia un de ses anciens mameluks nommé Othello, et que
celui-ci l’avait suivi à Viscovato: l’ex-roi de Naples songea à se faire
un agent de cet homme. Des relations de famille le rappelaient tout
naturellement à Castellamare; il lui ordonna d’y retourner, et le
chargea de lettres pour les personnes sur le dévoûment desquelles il
comptait le plus. Othello partit, arriva heureusement chez son beau-
père, et crut pouvoir lui tout dire; mais celui-ci, épouvanté, prévint la
police: une descente nocturne fut faite chez Othello et sa
correspondance saisie.
Le lendemain, toutes les personnes auxquelles étaient adressées
des lettres furent arrêtées et reçurent l’ordre de répondre à Murat
comme si elles étaient libres, et de lui indiquer Salerne comme le
lieu le plus propre au débarquement: cinq sur sept eurent la lâcheté
d’obéir, les deux autres, qui étaient deux frères espagnols, s’y
refusèrent absolument: on les jeta dans un cachot.
Cependant, le 17 septembre, Murat quitta Viscovato, le général
Franceschetti, ainsi que plusieurs officiers corses, lui servirent
d’escorte; il s’achemina vers Ajaccio par Cotone, les montagnes de
Serra et Bosco, Venaco, Vivaro, les gorges de la forêt de Vezzanovo
et Bogognone; partout il fut reçu et fêté comme un roi, et à la porte
des villes il reçut plusieurs députations qui le haranguèrent en le
saluant du titre de majesté; enfin le 25 septembre il arriva à Ajaccio.
La population tout entière l’attendait hors des murs; son entrée dans
la ville fut un triomphe; il fut porté jusqu’à l’auberge qui avait été
désignée d’avance par les maréchaux-de-logis: il y avait de quoi
tourner la tête à un homme moins impressionnable que Murat: quant
à lui, il était dans l’ivresse; en entrant dans l’auberge, il tendit la main
à Franceschetti.—Voyez, lui dit-il, à la manière dont me reçoivent les
Corses, ce que feront pour moi les Napolitains.—C’était le premier
mot qui lui échappait sur ses projets à venir, et dès ce jour même il
ordonna de tout préparer pour son départ.
On rassembla dix petites felouques: un Maltais, nommé Barbara,
ancien capitaine de frégate de la marine napolitaine, fut nommé
commandant en chef de l’expédition; deux cent cinquante hommes
furent engagés et invités à se tenir prêts à partir au premier signal.
Murat n’attendait plus que les réponses aux lettres d’Othello; elles
arrivèrent dans la matinée du 28. Murat invita tous les officiers à un
grand dîner, et fit donner double paye et double ration à ses
hommes.
Le roi était au dessert lorsqu’on lui annonça l’arrivée de monsieur
Maceroni: c’était un envoyé des puissances étrangères qui apportait
à Murat la réponse qu’il avait attendue si longtemps à Toulon. Murat
se leva de table et passa dans une chambre à côté. Monsieur
Maceroni se fit reconnaître comme chargé d’une mission officielle, et
remit au roi l’ultimatum de l’empereur d’Autriche. Il était conçu en
ces termes:

«Monsieur Maceroni est autorisé par les présentes à

prévenir le roi Joachim que sa majesté l’empereur d’Autriche
lui accordera un asile dans ses États, sous les conditions
suivantes:
«1o Le roi prendra un nom privé. La reine ayant adopté
celui de Lipano, on propose au roi de prendre le même nom.
»2o Il sera permis au roi de choisir une ville de la Bohême,
de la Moravie, ou de la Haute-Autriche, pour y fixer son
séjour. Il pourra même, sans inconvénient, habiter une
campagne dans ces mêmes provinces.
»3o Le roi engagera sa parole d’honneur envers S. M. I. et
R. qu’il n’abandonnera jamais les Etats autrichiens sans le
consentement exprès de l’empereur, et qu’il vivra comme un
particulier de distinction, mais soumis aux lois qui sont en
vigueur dans les Etats autrichiens.
»En foi de quoi, et afin qu’il en soit fait un usage
convenable, le soussigné a reçu l’ordre de l’empereur de
signer la présente déclaration.
Donné à Paris le 1er septembre 1815.
 Signé le prince de Metternich.»

Murat sourit en achevant cette lecture, puis il fit signe à monsieur

Maceroni de le suivre. Il le conduisit alors sur la terrasse de la
maison, qui dominait toute la ville et qui était dominée elle-même par
sa bannière qui flottait comme sur un château royal. De là on pouvait
voir Ajaccio toute joyeuse et illuminée, le port où se balançait la
petite flottille et les rues encombrées de monde, comme un jour de
fête. A peine la foule eut-elle aperçu Murat, qu’un cri partit de toutes
les bouches: Vive Joachim! vive le frère de Napoléon! vive le roi de
Naples! Murat salua, et les cris redoublèrent, et la musique de la
garnison fit entendre les airs nationaux. Monsieur Maceroni ne savait
s’il devait en croire ses yeux et ses oreilles. Lorsque le roi eut joui de
son étonnement, il l’invita à descendre au salon. Son état-major y
était réuni en grand uniforme: on se serait cru à Caserte ou à
Capodimonte. Enfin, après un instant d’hésitation, Maceroni se
rapprocha de Murat.
—Sire, lui dit-il, quelle réponse dois-je faire à sa majesté
l’empereur d’Autriche?
—Monsieur, lui répondit Murat avec cette dignité hautaine qui
allait si bien à sa belle figure, vous raconterez à mon frère François
ce que vous avez vu et ce que vous avez entendu; et puis vous
ajouterez que je pars cette nuit même pour reconquérir mon
royaume de Naples.
 III.
LE PIZZO.

Les lettres qui avaient déterminé Murat à quitter la Corse lui

avaient été apportées par un Calabrais nommé Luidgi. Il s’était
présenté au roi comme un envoyé de l’Arabe Othello, qui avait été
jeté, comme nous l’avons dit, dans les prisons de Naples, ainsi que
les personnes auxquelles les dépêches dont il était porteur avaient
été adressées. Ces lettres, écrites par le ministre de la police de
Naples, indiquaient à Joachim le port de la ville de Salerne comme
le lieu le plus propre au débarquement; car le roi Ferdinand avait
rassemblé sur ce point trois mille hommes de troupes autrichiennes,
n’osant se fier aux soldats napolitains, qui avaient conservé de
Murat un riche et brillant souvenir. Ce fut donc vers le golfe de
Salerne que la flottille se dirigea; mais, arrivée en vue de l’île de
Caprée, elle fut assaillie par une violente tempête, qui la chassa
jusqu’à Paola, petit port situé à dix lieues de Cosenza. Les bâtimens
passèrent en conséquence la nuit du 5 au 6 octobre dans une
espèce d’échancrure du rivage qui ne mérite pas le nom de rade. Le
roi, pour ôter tout soupçon aux gardes des côtes et aux scorridori[8]
siciliens, ordonna d’éteindre les feux et de louvoyer jusqu’au jour;
mais, vers une heure du matin, il s’éleva de terre un vent si violent,
que l’expédition fut repoussée en haute mer, de sorte que le 6, à la
pointe du jour, le bâtiment que montait le roi se trouva seul. Dans la
matinée il rallia la felouque du capitaine Cicconi, et les deux navires
mouillèrent à quatre heures de l’après-midi en vue de Santo-Lucido.
Le soir, le roi ordonna au chef de bataillon Ottoviani de se rendre à
terre pour y prendre des renseignemens. Luidgi s’offrit pour
l’accompagner, Murat accepta ses bons offices. Ottoviani et son
guide se rendirent donc à terre, tandis qu’au contraire, Cicconi et sa
felouque se remettaient en mer avec mission d’aller à la recherche
du reste de la flotte.
 Vers les onze heures de la nuit, le lieutenant de quart sur le
navire royal distingua au milieu des vagues un homme qui s’avançait
en nageant vers le bâtiment. Dès qu’il fut à la portée de la voix, il le
héla. Aussitôt le nageur se fit reconnaître: c’était Luidgi. On lui
envoya la chaloupe et il remonta à bord. Alors il raconta que le chef
de bataillon Ottoviani avait été arrêté, et qu’il n’avait échappé lui-
même à ceux qui le poursuivaient qu’en se jetant à la mer. Le
premier mouvement de Murat fut d’aller au secours d’Ottoviani; mais
Luidgi fit comprendre au roi le danger et l’inutilité de cette tentative;
néanmoins Joachim resta jusqu’à deux heures du matin agité et
irrésolu. Enfin, il donna l’ordre de reprendre le large. Pendant la
manœuvre qui eut lieu à cet effet, un matelot tomba à la mer et
disparut avant qu’on eût eu le temps de lui porter secours.
Décidément les présages étaient sinistres.
Le 7 au matin, on eut connaissance de deux bâtimens. Le roi
ordonna aussitôt de se mettre en mesure de défense; mais Barbara
les reconnut pour être la felouque de Cicconi et la balancelle de
Courrand, qui s’étaient réunies et faisaient voile de conserve. On
hissa les signaux, et les deux capitaines se rallièrent à l’amiral.
Pendant qu’on délibérait sur la route à suivre, un canot aborda le
bâtiment de Murat. Il était monté par le capitaine Pernice et un
lieutenant sous ses ordres. Ils venaient demander au roi la
permission de passer à son bord, ne voulant point rester à celui de
Courrand, qui, à leur avis, trahissait. Murat l’envoya chercher; et,
malgré ses protestations de dévoûment, il le fit descendre avec
cinquante hommes dans une chaloupe, et ordonna d’amarrer la
chaloupe à son bâtiment. L’ordre fut exécuté aussitôt, et la petite
escadre continua sa route, longeant, sans les perdre de vue, les
côtes de la Calabre; mais, à dix heures du soir, au moment où l’on
se trouvait à la hauteur du golfe de Sainte-Euphémie, le capitaine
Courrand coupa le câble qui le traînait à la remorque, et, faisant
force de rames, il s’éloigna de la flottille. Murat s’était jeté sur son lit
tout habillé: on le prévint de cet événement. Il s’élança aussitôt sur le
pont, et arriva à temps encore pour voir la chaloupe, qui fuyait dans
la direction de la Corse, s’enfoncer et disparaître dans l’ombre. Il
demeura immobile, sans colère et sans cris; seulement il poussa un