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lecture1b

lecture1b

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Published by achsanuddin
lecture on chemical bonding, electrostatic interactions, hydrogen bonding, van der Waals interactions
lecture on chemical bonding, electrostatic interactions, hydrogen bonding, van der Waals interactions

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Published by: achsanuddin on Dec 30, 2008
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11/07/2012

 
1 Intramolecular and intermolecular interactions
Central to our understandingof soft mattersystems are the interactions that makeit possiblefor atomsto form molecules and, on the other hand, forces that hold the various types of molecules togetheras condensed phases. The former result in
chemical bonds
, whereas the latter give rise to so-called
 physical bonds
. The fundamental difference between these two interactions is that in the formationof chemical bonds electron clouds of the bonding atoms are significantly redistributed. In the caseof physical bonds, only a slight perturbations of electron distributions takes place. These types of interactions are commonly referred to as
non-covalent 
interactions.In soft matter physics the relevant energy scale is thermal energy
B
, where
B
is the Boltzmannconstant (
1
.
381
×
10
23
J/K) and
is “room temperature”, something between 293 and 300 K,dependingon theauthor. Herewe willusethevalue298K, but notethat theexactvalueoftheambienttemperature - when picked from the range above - will not cause a huge quantitative variation in theinteraction energies in terms of 
B
. The thermal energy
B
can be taken as a rough measure for themagnitude of thermal forces in the system. These forces result from the random thermal motion andsubsequent collisions of atoms and molecules in the system. However, a more fundamental reason forthe use of 
B
as our energy scale in soft matter physics will become apparent in our review of basicthermodynamics and statistical mechanics.In this lecture we will first consider some aspects regarding chemical bonding, introducing theconcepts of purely and polar covalent bonds, and electronegativity (1.1). We then turn our attentionto electrostatic interactions between charges and dipoles, as these serve as useful models when tryingto understand interactions between real molecules (1.2). A special type of electrostatic interaction,the
hydrogen bond 
, is also introduced due to its immense importance in describing, for example, theproperties of water and three-dimensional structures of biological macromolecules (1.3). We end thisbrief review of basic interactions by finally considering the ubiquitous
van der Waals
forces betweenatoms and molecules (1.4).Clearly, the coverage of the material below is not exhaustive. Instead, we concentrate only on theissues essential to the later topics of this course. You can seek further insight on the topics at hand inmore specialized textbooks (see the list at the end of this text).1
 
Interatomic spacing
      E    n    e    r    g    y
ε
0
Figure 1:
Morse curve for two atoms forming a chemical bond. The equilibrium bond length r 
0
is theinteratomic distance where the energy is at minimum,
ε
.
1.1 Chemical bonding
By
chemical bonding
we mean the effect that causes the energy of two atoms close to each otherto be significantly lower, 100 kJ/mol or more, than when they are apart. The effect arises from thesharingoftheouter(valence)electronsoftheseatomswhich, inthepresenceoftwo ormorepositivelycharged nuclei, rearrange themselves into spatial distributions (orbitals) where the electrons are, onthe average, closer to the nuclei.It is common to represent the strength and length of a chemical bond (
i.e.
, distance between thebonding nuclei) with a so-called energy-distance Morse curve, see Fig. 1. The minimum energydistanceiscalledthe
equilibriumbondlength
,around whichthenucleivibrateaccording tothesystemtemperature. The
bond energy
(value of energy at the minimum) is then defined as the amount of energy required to increase the separation of the atoms forming the bond to infinity. However, whatis lacking from the Morse curves is the fact that chemical bonds, due to the redistributed electronclouds, have distinct directionality
1
. Probably the most widely used model for chemical bonding isthe
covalent bond 
or
shared electron
model.Different elements have different tendencies to draw electrons toward their nuclei. This ability iscalled
electronegativity
. Thus, in general the shared electron cloud is not evenly distributed in thespace between the bonding nuclei. Electronegativities cannot be directly measured, but the scalemost often used (developed by Linus Pauling) assigns fluorine the highest value, 4.0. The differencein the electronegativities of the bonding atoms then quantifies the extent how evenly or unevenlythe bond electrons are shared. A purely covalent bond (
i.e.
, completely evenly shared electrons)can only be obtained when the bonding atoms are of the same element. When the difference in theelectronegativities is large, the bond is said to posses
ionic
character or
polarity
. That is, we canview part of the electronic charge,
δ
, to be associated with the more electronegative atom,

 X 

.The atom with a smaller electronegativity,


, on the other hand, can be viewed as having a partial
1
There is a type of interatomic bonding known as the
metallic bonding
which has very little or even no directionality.However, this is not a topic of utmost importance to our course on soft matter.
2
 
positive charge
+
δ
, as the positive charge of its nuclei is not fully screened anymore by the valenceelectrons. The polar character of a chemical bond is typically expressed in the form
δ
δ
+
. Auseful, though approximative, way of looking at this effect is to think that there is a permanent dipoleassociated with the polar bond.The formation of one or more chemical bonds allows atoms to form energetically stable
molecules
which are characterized by their structure and composition. By stable we mean that the moleculesremain intact despite thermal collisions with other atoms and molecules. Since chemical bonds resultin increased localized electron densities, it can be assumed that the spatial regions associated withdifferent chemical bonds repel each other electrostatically. This way of thinking, known as the
“valence shell electron repulsion”
(VSEPR) model is quite good at explaining the shapes of variousmolecules
2
.
1.2 Electrostatic interactions
As became apparent from our discussion on chemical bonds above, many molecules contain polarchemical bonds that can be associated with electic dipoles, comprising of atomic “partial charges”
±
δ
. The molecules, in turn, as collections of these partial charges, can be associated with electricdipoles, quadrupoles, and higher multipoles. On the other hand, solvation of salt in an aqueousenvironment introduces ionized atoms, such as Na
+
and Cl
, into the system. Many chemical groupsin molecules may also be charged (
e.g.
, protonated and de-protonated) at certain values of pH of thehost medium.All in all, we see that electrostatic effects are important in a wide range of molecular systems
3
. Itturns out that relating the intricate intermolecular forces to simple electrostatic interactions betweencharges, dipoles, and higher multipoles works surprisingly well in understanding the strcuture anddynamics of condensed matter systems. In particular, in soft matter even the weakest intermolecularforces are comparable to
B
, and may play an important role in the behavior of the system studied.Hence, in the following we will review the very basic electrostatic interactions between groups of charged particles.
1.2.1 Charge-charge interaction
The simplest, as well as the strongest, electrostatic interaction we will study is the one between twocharges
Q
1
and
Q
2
. From basic electrostatics we recall the interaction energy to be
(
) =
Q
1
Q
2
4
πε
0
ε
=
z
1
 z
2
e
2
4
πε
0
ε
,
(1)
2
As a final note on chemical bonds,you may thinkthat orbitals, the spatial representationsof the atomic and molecularelectron distributions, are only useful “tools” for carrying out quantum-mechanical calculations. However, a numberof recent experimental studies using weak laser pulses have allowed researchers to “map” the electron distributions of different molecules. And yes, the obtained spatial electron probability distributions are in excellent agreement with theorbital model.
3
 All
intramolecular and intermolecular effects are ultimately electronic effects!
3

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