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+ 5.1 eV Na+ +
(ionization energy)
∞
Cl + - + 3.6 eV
Cl
(electron affinity)
∞
Cl Cl
r0 (electrostatic energy)
How to find r0 ?
1 e2
Ei ECoul Erepuls B exp(r / ) minimum
40 r
r0 2
r0
Neither contact between cations (Na+ ) nor contact between anions (Cl- )
3 r0
r0
2 r0
Total Coulomb energy per ion pair: Ecoul
Madelung Constants
Ecoul= E( 6 Cl nearest neighbors at distance r ) + E( 12 Na
-
0
+
nearest neighbors at distance 2 r0 )
+ E( 8 Cl- at distance 3 r0 )+…
e2 12 8
Ecoul 6 ...
40r0 2 3
e2
Ei C e r/
4 0 r
t ers
r ame
a
np
dEi now
However: condition 0 un
k
dr r=r
0
dEi e2 C r0 /
determination of,e.g., C e 0
dr r r0 4 r 2
00
e2 r0 / e2
C e Ei C er / r0 r
40r0 2 40r 2
e r
Ei 1 2 e
40r r0
e 2 ?
Ei @ r=r0 Ei 1
40r0 r0 Input from
experiment
Click here for response functions in gases.
Note that the bulk modulus B is inverse proportional to the bulk compressibility
1 dV
bulk compressibility since NaCl cubic xx yy zz
V dp
1 NaCl-molecule requires
V 2 r 3 ̂ +
r
Click for details. Note special sign convention in thermodynamics
dE dE dr 1 dE dp d 1 dE 1 d2E 1 dE
p 2 2
dV dr dV 6r dr dr dr 6r dr 6r 2 dr 2 3r 3 dr
dr 1 1 d2E
2 dp
dV 6r 2 2
dr r r0 6r0 dr r r
0
Let´s remember
1 dV 1 dV dr 6r 2 dr 3 dr dp 3
3
V dp V dr dp 2r dp r dp dr r r0 r0
d2E 18r0
2
dr r r0
2 2
r0 r
18r0 d E 2
d e r
2 2 1 2 e
dr r r0 dr 4 0r r
0 r r0
1
r0 720 r0 4 Cohesive energie
2
e2 (can be experimentally determined via Born-Haber cycle)
Click for detailed information
In general bond neither covalent nore pure ionic Mixed ionic-covalent bonds
cov ion
Ĥd
determined from E Min.
d
δ+ δ-
A + B A B
δ+ δ- 1/2
E( A B ) > [E( A A ) E( B B )]
empirical formula
1
better than E( AA ) E(BB)
2
Linus Pauling
is the only person ever to receive two unshared Nobel Prizes
—for Chemistry (1954) and for Peace (1962).
Find here Pauling’s electronegativity
online
2
% ionicity of bond 100
1 2
A B
A B
2
2
% ionicity of bond 1001 e