A Matter of Density: Exploring the Electron Density Concept in the Chemical, Biological, and Materials Sciences

353 Pages·2012·20.098 MB·English

by  N. Sukumar

A MATTER OF DENSITY

A MATTER OF DENSITY
Exploring the Electron Density
Concept in the Chemical, Biological,
and Materials Sciences
Edited by
N. SUKUMAR
Department of Chemistry
Shiv Nadar University
Dadri, UP, India
A JOHN WILEY & SONS, INC., PUBLICATION
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LibraryofCongressCataloging-in-PublicationData:
Amatterofdensity:exploringtheelectrondensityconceptinthechemical,biological,and
materialssciences/editedbyN.Sukumar.
pagescm
Includesindex.
ISBN978-0-470-76900-3(hardback)
1.Electrondistribution.I.Sukumar,N.,editorofcompilation.
QC793.5.E626M382013
539.7(cid:2)2112—dc23
2012023635
PrintedintheUnitedStatesofAmerica
ISBN:9780470769003
10987654321
CONTENTS
Preface vii
Contributors ix
1 Introduction of Probability Concepts in Physics—The Path
to Statistical Mechanics 1
N.Sukumar
2 Does God Play Dice? 15
N.Sukumar
3 The Electron Density 41
N.SukumarandSunandaSukumar
4 Atoms in Molecules 67
N.Sukumar
5 Density Functional Approach to the Electronic Structure
of Matter 107
N.Sukumar
6 Density-Functional Approximations for Exchange
and Correlation 125
ViktorN.Staroverov
v
vi CONTENTS
7 An Understanding of the Origin of Chemical Reactivity
from a Conceptual DFT Approach 157
ArindamChakraborty,SomaDuley,SantanabGiri,andPratimKumar
Chattaraj
8 Electron Density and Molecular Similarity 203
N.Sukumar
9 Electrostatic Potentials and Local Ionization Energies
in Nanomaterial Applications 233
PeterPolitzer,FelipeA.Bulat,JamesBurgess,JeffreyW.Baldwin,andJane
S.Murray
10 Probing Electron Dynamics with the Laplacian
of the Momentum Density 257
PrestonJ.MacDougallandM.CreonLevit
11 Applications of Modern Density Functional Theory
to Surfaces and Interfaces 271
G.Pilania,H.Zhu,andR.Ramprasad
Index 313
PREFACE
Electron density is one of the fundamental concepts underpinning modern
chemistry. Introduced through MaxBorn’s probability interpretation of the wave
function, it is an enigma that bridges the classical concepts of particles and
fluids. The electronic structure of matter is intimately related to the quantum
laws of composition of probabilities and the Born–Oppenheimer separation
of electronic and nuclear motions in molecules. The topology of the electron
density determines the details of molecular structure and stability. The electron
density is a quantity that is directly accessible to experimental determination
through diffraction experiments. It is the basic variable of density functional
theory, which has enabled practical applications of the mathematical theory
of quantum physics to chemical and biological systems in recent years. The
importance of density functional theory was recognized by the 1998 Nobel Prize
in chemistry to Walter Kohn and John Pople.
Inthefirstpart(Chapters1–6)ofthisbook,weaimtopresentthereaderwith
a coherent and logically connected treatment of theoretical foundations of the
electron density concept, beginning with its statistical underpinnings: the use of
probabilitiesinstatisticalphysics(Chapter1)andtheoriginsofquantummechan-
ics. We delve into the philosophical questions at the heart of the quantum theory
such as quantum entanglement (Chapter 2), and also describe methods for the
experimentaldeterminationofelectrondensitydistributions(Chapter3).Thecon-
ceptual and statistical framework developed in earlier chapters is then employed
totreatelectronexchangeandcorrelation,thepartitioningofmoleculesintoatoms
(Chapter 4), density functional theory, and the theory of the insulating state of
matter (Chapter 5). Chapter 6 concludes with an in-depth treatment of density-
functional approximations for exchange and correlation by Viktor Staroverov.
The second part (Chapters 7–11) deals with applications of the electron
density concept in chemical, biological, and materials sciences. In Chapter 7,
Chakraborty, Duley, Giri, and Chattaraj describe how a deep understanding of
the origins of chemical reactivity can be gleaned from the concepts of density
vii
viii PREFACE
functionaltheory.Applicationsofelectrondensityinmolecularsimilarityanalysis
and of electron-density-derived molecular descriptors form the subject matter of
Chapter8.InChapter9,Politzer,Bulat,Burgess,Baldwin,andMurray,elaborate
on two of the most important such descriptors, namely, electrostatic potentials
and local ionization energies, with particular reference to nanomaterial applica-
tions. All the applications discussed thus far have dealt with electron density
in position space. A complementary perspective is obtained by considering the
electron density in momentum space. MacDougall and Levit illustrate this in
Chapter 10, by employing the Laplacian of the electron momentum density as a
probe of electron dynamics. Pilania, Zhu, and Ramprasad conclude the discus-
sion in Chapter 11 with some applications of modern density functional theory
to surfaces and interfaces. The book is addressed to senior undergraduate and
graduate students in chemistry and philosophers of science, as well as to current
andaspiringpractitionersofcomputationalquantumchemistry,andanyoneinter-
ested in exploring the applications of the electron density concept in chemistry,
biology, and materials sciences.
I would like to express my sincere thanks and appreciation to the numerous
friends and colleagues who helped to make this book a reality by graciously
contributingtheirprecioustimeanddiligenteffortsinreviewingvariouschapters
or otherwise offering their valuable suggestions, namely, Drs. Felipe Bulat and
A. K. Rajagopal (Naval Research Laboratory, Washington, DC), Prof. Shridhar
Gadre (University of Pune and Indian Institute of Technology, Kanpur, India),
Dr. Michael Krein (Lockheed Martin Advanced Technology Laboratories,
Cherry Hill, NJ and Rensselaer Polytechnic Institute, Troy, NY), Prof. Preston
MacDougall (Middle Tennessee State University, Murfreesboro, TN), Prof.
Cherif Matta (Mount Saint Vincent University and Dalhousie University,
Halifax, Nova Scotia, Canada), Dr. Salilesh Mukhopadhyay (Feasible Solutions,
NJ), Profs. Peter Politzer and Jane Murray (CleveTheoComp LLC, Cleveland,
OH), Prof. Sunanda Sukumar (Albany College of Pharmacy, Albany, NY and
Shiv Nadar University, Dadri, India), Prof. Ajit Thakkar (University of New
Brunswick, Fredericton, Canada), and Prof. Viktor Staroverov (University of
Western Ontario, Canada). I also owe a deep debt of gratitude to the institutions
and individuals who hosted me at various times during the last couple of years
and provided me with the facilities to complete this book, namely, Rensselaer
Polytechnic Institute in Troy, NY, and my host there Prof. Curt Breneman; the
Institute of Mathematical Sciences in Chennai, India, and my host there Prof. G.
Baskaran; and Shiv Nadar University in Dadri, India. The patient assistance of
Senior Acquisitions Editor, Anita Lekhwani, and her very capable and efficient
team at John Wiley & Sons has also been invaluable in this process.
N. Sukumar
DepartmentofChemistry
ShivNadarUniversity
Dadri,UP,India
CONTRIBUTORS
Jeffrey W. Baldwin, Acoustics Division, Naval Research Laboratory,
Washington, DC
FelipeA.Bulat,AcousticsDivision,NavalResearchLaboratory,Washington,DC
JamesBurgess,AcousticsDivision,NavalResearchLaboratory,Washington,DC
Arindam Chakraborty, Department of Chemistry and Center for Theoretical
Studies, Indian Institute of Technology, Kharagpur, India
Pratim Kumar Chattaraj, Department of Chemistry and Center for Theoretical
Studies, Indian Institute of Technology, Kharagpur, India
SomaDuley,DepartmentofChemistryandCenterforTheoreticalStudies,Indian
Institute of Technology, Kharagpur, India
Santanab Giri, Department of Chemistry and Center for Theoretical Studies,
Indian Institute of Technology, Kharagpur, India
M. Creon Levit, NASA, Advanced Supercomputing Division, Ames Research
Center, Moffett Field, CA
PrestonJ.MacDougall,DepartmentofChemistryandCenterforComputational
Science, Middle Tennessee State University, Murfreesboro, TN
Jane S. Murray, CleveTheoComp LLC, Cleveland, OH
G. Pilania, Department of Chemical, Materials and Biomolecular Engineering,
Institute of Materials Science, University of Connecticut, Storrs, CT
Peter Politzer, CleveTheoComp LLC, Cleveland, OH
ix