London dispersion forces in molecules, solids and nano-structures: an introduction to physical models and computational methods

456 Pages·2020·11.585 MB·English

by  Ángyán, János, Dobson, John, Gould, Tim, Hirst, Jonathan, Jansen, Georg

London Dispersion Forces in Molecules, Solids and
Nano- structures
An Introduction to Physical Models and Computational Methods
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Theoretical and Computational Chemistry Series
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Jonathan Hirst, University­of­Nottingham,­Nottingham,­UK
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97 1: Knowledge- based Expert Systems in Chemistry: Not Counting on
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3 Computers
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c.or 4: Computational Nanoscience
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14: Self- organized Motion: Physicochemical Design based on Nonlinear
Dynamics
15: Knowledge- based Expert Systems in Chemistry: Artificial Intelligence in
Decision Making
16: London Dispersion Forces in Molecules, Solids and Nano-s tructures: An
Introduction to Physical Models and Computational Methods
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London Dispersion Forces
in Molecules, Solids and
1 Nano-s tructures
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6 An Introduction to Physical Models
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sc. János Ángyán
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on Griffith­University,­Australia
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April Georg Jansen
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Tim Gould
Griffith­University,­Australia
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86 Theoretical and Computational Chemistry Series No. 16
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82 Print ISBN: 978-1 - 78262- 045- 7
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0 Print ISSN: 2041- 3181
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1- Dedication
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or patient collaborator and dear friend.
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Theoretical and Computational Chemistry Series No. 16
London Dispersion Forces in Molecules, Solids and Nano- structures: An Introduction to  
Physical Models and Computational Methods
By János Ángyán, John Dobson, Georg Jansen and Tim Gould
© János Ángyán, John Dobson, Georg Jansen and Tim Gould 2020
Published by the Royal Society of Chemistry, www.rsc.org
v
View Online
vi Dedication
János was born in Pecs, Hungary, but spent most of his early life in Buda-
pest where he studied chemistry and obtained doctoral degrees. After post-
doctoral stays in Toronto and Paris he took up a Humboldt fellowship in
Stuttgart and Bonn, Germany. Immediately thereafter János took a posi-
tion with the French CNRS and was based from 1991 at Nancy University
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00 (now University of Lorraine). He obtained his Habilitation in 1996 and later
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1-F became Director of Research. During all this time he collaborated intensely
86 with the Theoretical Chemistry Laboratory of the University of Paris (Pierre
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62 et Marie Curie, Sorbonne) and held honorary guest professorships in Vienna
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78 and Budapest. In addition to his seminal publications (167) in theoretical
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78 chemistry, he organised a number of collaborations and international con-
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9/ ferences and was on several journal Editorial Boards. Before the present
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oi:1 János, either since the days of his Humboldt fellowship (Georg) or through
g | d the French-Australian FAST research programme (John and Tim). We have
or excellent memories from our numerous mutual encounters in Europe and
c.
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n János’s health condition, which was already somewhat delicate.
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20 The last time that the combined authors saw János was at a CECAM con-
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01 János had a major surgical procedure that we all hoped would give him
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he uary 22, 2017, at age 60.
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1- Preface
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0. This book is focussed on the theory and modelling of dispersion forces.
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c.or effects can be dominant, just as is the case for gravity, another weak attrac­
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s.r tive force.
ub There are various texts1–6 dealing with dispersion interactions, primar­
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s:// ily from the macroscopic, field­ oriented viewpoint. These works typically
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A in detail the interactions down to intimate contact where atomic­ level,
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sh to intimate contact, Adrian Parsegian says on page 35 of his book:6 “these
ubli are at best approximations and at worst only mind games”. This region of
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intimate contact is very important and is a major focus of this book. To
treat it properly we are led into some fairly challenging areas of quantum
chemistry and condensed matter physics involving significant numerical
computation. Reliable, computable predictive methods are only beginning
to appear.
There are also a number of chemically oriented texts7–9 on intermolecular
interactions in general, with dispersion interactions of course included.
However, not much is available with an exclusive focus on dispersion
forces, including realistic treatment of atoms, molecules, nano­ structures
and bulk matter. This coverage requires both the coarse­g rained and fine­
grained levels of description. This is the scope of the present book.

Theoretical and Computational Chemistry Series No. 16
London Dispersion Forces in Molecules, Solids and Nano- structures: An Introduction to  
Physical Models and Computational Methods
By János Ángyán, John Dobson, Georg Jansen and Tim Gould
© János Ángyán, John Dobson, Georg Jansen and Tim Gould 2020
Published by the Royal Society of Chemistry, www.rsc.org
vii
View Online
viii Preface
We aim to cover the physics, chemistry and mathematics of dispersion
forces, starting from qualitative ideas, and a minimal undergraduate knowl­
edge of mathematics and science, and developing all approaches up to the
current state of the art. A synthesis of physical and chemical approaches is
required in order to provide a seamless coverage of these interactions at all
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00 separations between the interacting bodies.
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1-F This is a very large area to cover, and in order to do so we have decided to
86 provide only minimal coverage of the effects of electromagnetic retardation
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62 or thermal effects on the electromagnetic field itself, as these are very well
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oi:1 The book is organised as follows. The first two chapters give a general and
g | d historical introduction, followed by an outline of the major phenomena and
or concepts, at a simple and highly intuitive level. The next few chapters pres­
c.
s ent the major theoretical methods in some detail, starting from a relatively
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b low level and building up to the state of the art. Then there are some chap­
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n approaches. A summary chapter suggests practical software choices for mod­
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e
h
s
bli 1. S. Y. Buhmann, Dispersion Forces I: Macroscopic Quantum Electrodynamics
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P and Ground-S tate Casimir, Casimir–Polder and van der Waals Forces, Num­
ber 247 in Springer Tracts in Modern Physics, Springer, 2012.
2. J. N. Israelachvili, Intermolecular and Surface Forces, Academic Press, 2011.
3. D. Langbein, Theory of Van der Waals Attraction, Springer Tracts in Modern
Physics, Springer­ Verlag, Berlin, 1974.
4. J. Mahanty and B. W. Ninham, Dispersion Forces. Academic Press, London,
1976.
5. B. W. Ninham and P. L. Nostro, Molecular Forces and Self­A ssembly, in Col-
loid, Nano Sciences and Biology, Cambridge University Press, Cambridge,
2010.
6. V. A. Parsegian, van der Waals Forces: a Handbook for Biologists, Chemists,
Engineers, and Physicists. Cambridge University Press, Cambridge, 2006.
7. I. G. Kaplan, Intermolecular Interactions: Physical Picture, Computational
Methods and Models, Wiley, Chichester, 2006.
8. J. S. Rowlinson, Cohesion: A Scientific History of Intermolecular Forces,
Cambridge University Press, Cambridge, 2002.
9. A. J. Stone, The Theory of Intermolecular Forces, Oxford University Press,
Oxford, 1997.
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61- Acknowledgments
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0. We acknowledge support from several organisations. (i) CNRS (Cen-
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oi: tre National de la Recherche Scientifique) through the PICS program
d
g | “2DvdW”, (ii) Griffith University, University of Lorraine, University of
c.or Duisburg- Essen for hospitality and financial support, (iii) FAST (France-
s
s.r Australia Science and Technology) cooperation scheme of the French and
b
pu Australian governments, (iv) CECAM (Centre Européen de Calcul Atom-
s:// ique et Moléculaire). All of us have greatly appreciated the patience and
p
htt support of our families, partners and students while we worked on the
n
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Theoretical and Computational Chemistry Series No. 16
London Dispersion Forces in Molecules, Solids and Nano- structures: An Introduction to  
Physical Models and Computational Methods
By János Ángyán, John Dobson, Georg Jansen and Tim Gould
© János Ángyán, John Dobson, Georg Jansen and Tim Gould 2020
Published by the Royal Society of Chemistry, www.rsc.org
ix
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1- Contents
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ed 1.4.6 1940s: Electromagnetic Retardation and the
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blis Casimir Effect 6
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Colloids 7
1.4.8 1950s and 1960s: Macroscopic Lifshitz Theory 7
1.4.9 1960s Onwards: Extending Lifshitz to
Non- planar Geometries 8
1.4.10 1950s Onwards: is There Life after Lifshitz? 8
1.4.11 1960s–Present: Dispersion Forces via the
Physics of Many Interacting Electrons 8
1.4.12 1960s Onwards: Many- electron Quantum
Perturbation Theory 9

Theoretical and Computational Chemistry Series No. 16
London Dispersion Forces in Molecules, Solids and Nano- structures: An Introduction to  
Physical Models and Computational Methods
By János Ángyán, John Dobson, Georg Jansen and Tim Gould
© János Ángyán, John Dobson, Georg Jansen and Tim Gould 2020
Published by the Royal Society of Chemistry, www.rsc.org
xi