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 The energy of a molecule can

be expressed simply as the


sum of electronic, vibrational
and rotational contributions.
 Electric dipole moments are symmetrical and cancel out.

𝛍′ 𝛍
𝛍 𝛍′
O C O
χO = 3.44 χC = 2.55 χO = 3.44
𝛍′ ′

μ =μ
μ′′ = μ′ = μ
Δμ = 0
𝛍
Δμ = 0
𝛍
𝛍
𝛍
𝛍
𝛍

Δμ = 0
 Electric dipole moments are asymmetrical and cannot be cancel.
 Molecule has a resultant electric dipole moment.

𝛍′ 𝛍

O C S 𝛍 𝛉 𝛍
χO = 3.44 χ = 2.55
C χS = 2.58

μ′ > 𝜇
Δμ ≠ 0
𝜇𝑟𝑒𝑠 = 2𝜇2 + 2𝜇2 cos 𝜃
Cl
𝝁′ 𝝁′

𝝁′

𝛍
𝛍

μ′ > μ μ′ > μ
Δμ ≠ 0 Δμ ≠ 0
Δμ = μres = 1.57 D Δμ = μres = 2μ2 + 2μ2 cos θ

μres = 2μ2 + 2μ2 cos 60

μres = 3μ2 = 3 × 1.57 D


𝝁′ 𝝁′
𝛍

𝝁′

𝛍 𝝁′

μ′ > μ Δμ = μres = 0
Δμ ≠ 0
Δμ = μres = 2μ2 + 2μ2 cos θ

μres = 2μ2 + 2μ2 cos 120

μres = μ2 = 1.57 D
𝛍𝐳

μres = μ2z + μ2x + μ2y

𝛍𝐱

μx = QiRi
𝛍𝐲 i

where Q i is the partial charge of atom i and R i is the distance


of that particular charge from the origin
 Two charges separated by distance r in the vacuum, the
Coulomb potential is given by:
q1 q 2
V=
4πεo r r
 If its immersed in a particular medium, the Coulomb potential is
given by:
q1 q 2
V=
4πεr
 The relative permittivity is given by:
ε
εr =
εo
Large relative Highly Polarizable
permittivity (polar)
 The quantitative relation between the relative permittivity and
the electric properties of the molecule is expressed by the Debye
equation:

εr − 1 ρPM
=
εr + 1 M
where ρ is the mass density of the sample, M is the molar mass of the
sample and PM is the molar polarization, its given by:

NA μ2
PM = α+
3εo 3KT
where NA is the Avogadro constant, α is the polarizability, K is the
Boltzmann constant and T is the absolute temperature.
PM
NA μ2 1 NA α
PM = × +
9εo K T 3εo

y = m x + c NA μ2
θ tan θ =
9εo K
NA α
9εo K tan 𝜃 3εo c 3εo
μ= α=
NA NA
1
T

εr − 1 ρNA μ2 1 ρNA α
= × +
εr + 1 9εo K T 3Mεo

εr − 1 ρNA α
If 𝜇 = 0 = Clausius-Mossotti equation
εr + 1 3Mεo
 It’s a measure of the ability of a molecule to undergo a
redistribution of charge in response to the application of an
electric field.
 Non-polar molecule may acquire an induced dipole moment (μ∗ )
when they are exposed to an electric field.
 Induced dipole moment is given by :
μ∗ = α E
where μ∗ induced dipole moment, α is the polarizability and 𝐸 is the
applied electric field.
 The SI unit of the polarizability is C 2 m2 J −1 .
 Polarizability is often expressed as a polarizability volume (𝛼 ′ )
𝛼
𝛼′ =
4𝜋𝜀𝑜
 Polarizability volumes correlate with the HOMO – LUMO
separation in atoms or molecules


1
α ∝
Separation between HOMO − LUMO

LUMO
LUMO

HOMO
HOMO
Typically high α′ Typically low α′
 Polarization is the electric dipole moment density

P= μ ℵ

where μ is the mean electric dipole moment and ℵ is the number density.

 The orientation polarization arises from the permanent dipole

moment.

 The distortion polarization arises from the distortion of the

positions of the nuclei by the applied electric field.


 Some molecules & ions possess permanent magnetic dipole
moments.
 An applied magnetic field can induce the magnetic moment.
 Entire solid sample becomes magnetized
 The magnetization of the solid sample is given by:
M = χH
where M is the magnetization, χ is the volume magnetic susceptibility
and His the magnetic field strength.
 A closely related quantity of molar magnetic susceptibility (χm ) is
given by:
χm = χVm
where Vm is the molar volume of the substance.
 Molecules & ions with a permanent magnetic dipole moment (m)
contributes to the magnetization.
m2
M∝
3KT
 The molar magnetic susceptibility can be rewritten as
m2
χ = ℵμ0 ξ+
3KT
where ξ is the magnetizability and ℵ is the number density.
N nNA
ℵχ = Vm = Vm = NA
V nVm
where 𝑛 is the number of moles and N is the total number of molecules
or atoms.
m2 m2
χm = χ 𝑉𝑚 = ℵVm μ0 ξ+ = NA μ0 ξ +
3KT 3KT
 The magnetic flux density (B) is given by:
B = μo H + M
where μo is the vacuum permeability (μo = 4π × 10−7 J C −2 m−1 s 2
B = μo H + χH = μo H 1 + χ

M H M H

𝜒>0 𝜒<0

B B
 The permanent magnetic moment arises from any unpaired
electron spins.
 The magnetic moment of electron is given by:

where ge is the g-value of the electron (ge = 2.002319).

 Several unpaired electron spins in each molecule or ion, the


magnetic moment is rewritten as:

where S is the total spin of the electrons in the molecule or ion


 The spin contribution to the molar magnetic susceptibility is
given by:

 In the absence of applied magnetic field ( )

Applied
Field M H
Diamagnetic

LUMO
HOMO

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