Chapter 20 +21.
A lot of biomolecular interactions involve interactions
between electrical charges
Chapter 20. Coulomb’s Law of Electrostatic Forces
Coulomb’s Law
∁𝑞1 𝑞2
𝑢(𝑟) = 1
𝑟 ∁=
4𝜋𝜀𝑜
Interaction energy between two charges in vacuum
𝜀𝑜 - permittivity of vacuum, SI 𝜀𝑜 = 8.85 × 10−12 F m−1
Charge interactions are long range (1/r)
∁𝑞1 𝑞2
𝑢(𝑟) =
𝐷𝑟
𝐷 – dielectric constant
𝐷 = 1.00059 air (@ 0oC)
𝐷 = 78.54 water (@ 25oC)
Chapter 20. Coulomb’s Law of Electrostatic Forces
The Bjerrum length 𝑙𝐵 , separation at which Coulomb energy 𝑢(𝑟) between mole of ions pairs
is equal to RT
∁𝑒 2 𝑁
𝑙𝐵 = 𝑙𝐵,𝑎𝑖𝑟 = 560 Å 𝑙𝐵,𝑤𝑎𝑡𝑒𝑟 = 7.13 Å
𝐷𝑅𝑇
Chapter 20. Coulomb’s Law of Electrostatic Forces
Electrostatic forces
𝜕 𝑢 ∁𝑞1 𝑞2
𝑓=− =
𝜕𝑟 𝐷𝑟 2
∁𝑞1 𝑞2 𝑟21 𝑟21 Unit vector pointing from 𝑞 to 𝑞 , 𝑓ഥ force on 𝑞
ഥ
𝑓1 = 2 1 1 1
𝐷𝑟 2 𝑟 𝑟
𝑓ഥ1 =−𝑓2
Electrostatic fields
Set of vectors that describe
the force per unit charge
∁ 𝑞𝑖 𝑟ഥ𝑖
𝐸ത = 2
𝐷 𝑟𝑖 𝑟𝑖
𝑖
Chapter 20. Coulomb’s Law of Electrostatic Forces
Gauss Law
1 1
𝛷 = ර 𝐷 𝐸ത ∙ 𝑑𝑠ҧ = 𝑞𝑖 = ශ 𝜌 𝑑𝑉
𝜀𝑜 𝜀𝑜
𝑖
Chapter 21. The Electrostatic Potential
𝑑𝑤 = −𝑓 ҧ ∙ d𝑙 ҧ = −𝑞 𝐸ത ∙ d𝑙 ҧ
𝐵 We assume no heat exchange, hence,
𝑤𝐴𝐵 = −𝑞 න 𝐸ത ∙ d𝑙 ҧ 𝑤𝐴𝐵 is the maximum possible work and
𝐴
is called the reversible work
Define the difference in the electrostatic potentials 𝜓𝐴 and 𝜓𝑏
as the work 𝑤𝐴𝐵 of moving unit charge
𝐵
𝜓𝐴 − 𝜓𝐵 = 𝑤𝐴𝐵 /𝑞 = න 𝐸ത ∙ d𝑙 ҧ 𝐸ത = −∇𝜓 𝜓∞ = 0
𝐴
Example, the electrostatic potential around a point charge 𝑞𝑓𝑖𝑥𝑒𝑑 or fixed charge density
𝑞𝑓𝑖𝑥𝑒𝑑 𝑞𝑓𝑖𝑥𝑒𝑑 𝜌
𝜓(𝑟) = 𝜓(𝑟) = ශ 𝑑𝑉
4𝜋𝜀𝑜 𝐷𝑟 4𝜋𝜀𝑜 𝐷 𝑟
Chapter 21. The Electrostatic Potential
Equipotential surfaces
Chapter 21. The Electrostatic Potential
Electrostatic Interactions are Conservative Forces
The reversible electrostatic work is path-independent
The work of moving a charge around a cycle is zero
𝐵
𝜓𝐴 − 𝜓𝐵 = 𝑤𝐴𝐵 /𝑞 = න 𝐸ത ∙ d𝑙 ҧ
𝐴
Chapter 21. The Electrostatic Potential
Electrostatic Interactions are Conservative Forces
The reversible electrostatic work is path-independent
The work of moving a charge around a cycle is zero
𝐵
𝜓𝐴 − 𝜓𝐵 = 𝑤𝐴𝐵 /𝑞 = න 𝐸ത ∙ d𝑙 ҧ
𝐴
Chapter 21. The Electrostatic Potential
Dipoles
𝜇ҧ = 𝑞d𝑙 ҧ Dipole moment
𝑙 is fixed
Energy of a dipole in an electric field
𝑤 = 𝐸𝜇 cos 𝜃 − 1
Chapter 21. The Electrostatic Potential
Voltage-gated ion channels
Ions (sometimes) can cross biological membranes in
one direction but not the other
Egg cell membrane of a starfish
Chapter 21. The Electrostatic Potential
Voltage-gated ion channels
Ions (sometimes) can cross biological membranes in
one direction but not the other
Egg cell membrane of a starfish
Chapter 21. The Electrostatic Potential
𝑝𝑜𝑝𝑒𝑛
= 𝑒 −(Δ𝐺0−𝑤)/𝑅𝑇
𝑝𝑐𝑙𝑜𝑠𝑒𝑑
Δ𝐺0 - energy needed to open the channel
𝑤 - work performed by the field by orienting the dipole
𝜓𝑞𝑙
𝑤 𝜃 = 𝐸𝑞𝑙 (cos 𝜃𝑐𝑙𝑜𝑠𝑒𝑑 − cos 𝜃𝑐𝑙𝑜𝑠𝑒𝑑 ) = − (Δ cos 𝜃)
𝑑
𝑞, 𝑙, Δ cos 𝜃 , 𝑑 might not be knows independently
𝜓𝑞𝑙
𝑧𝑒𝑓𝑓 𝑒 = − (Δ cos 𝜃)
𝑑
𝑝𝑜𝑝𝑒𝑛 1 1
𝐼~ = =
𝑝𝑜𝑝𝑒𝑛 + 𝑝𝑐𝑙𝑜𝑠𝑒𝑑 1 + 𝑝𝑐𝑙𝑜𝑠𝑒𝑑 /𝑝𝑜𝑝𝑒𝑛 1 + 𝑒 −(Δ𝐺0 −𝑧𝑒𝑓𝑓 𝑒𝜓)/𝑅𝑇
Chapter 21. The Electrostatic Potential
𝑝𝑜𝑝𝑒𝑛 1 1
𝐼~ = =
𝑝𝑜𝑝𝑒𝑛 + 𝑝𝑐𝑙𝑜𝑠𝑒𝑑 1 + 𝑝𝑐𝑙𝑜𝑠𝑒𝑑 /𝑝𝑜𝑝𝑒𝑛 1 + 𝑒 −(Δ𝐺0−𝑧𝑒𝑓𝑓 𝑒𝜓)/𝑅𝑇
Chapter 21. The Electrostatic Potential
𝑝𝑜𝑝𝑒𝑛 1 1
𝐼~ = =
𝑝𝑜𝑝𝑒𝑛 + 𝑝𝑐𝑙𝑜𝑠𝑒𝑑 1 + 𝑝𝑐𝑙𝑜𝑠𝑒𝑑 /𝑝𝑜𝑝𝑒𝑛 1 + 𝑒 −(Δ𝐺0−𝑧𝑒𝑓𝑓 𝑒𝜓)/𝑅𝑇
Chapter 21. The Electrostatic Potential
𝑝𝑜𝑝𝑒𝑛 1 1
𝐼~ = =
𝑝𝑜𝑝𝑒𝑛 + 𝑝𝑐𝑙𝑜𝑠𝑒𝑑 1 + 𝑝𝑐𝑙𝑜𝑠𝑒𝑑 /𝑝𝑜𝑝𝑒𝑛 1 + 𝑒 −(Δ𝐺0−𝑧𝑒𝑓𝑓 𝑒𝜓)/𝑅𝑇
Chapter 21. The Electrostatic Potential
Potential field around a dipole
∁𝜇ҧ ∙ (𝑟/𝑟)
ҧ ∁𝜇𝑄 cos 𝜃
𝜓= 𝑢(𝑟, 𝜃) =
𝐷𝑟 2 𝐷𝑟 2
Chapter 21. The Electrostatic Potential
Poisson’s equation
Gauss divergence theorem
ර 𝑣ҧ ∙ 𝑑𝑠ҧ = ශ ∇ ⋅ 𝑣𝑑𝑉
ҧ 𝑣ҧ = 𝐷𝐸ത
ර 𝐷𝐸ത ∙ 𝑑 𝑠ҧ = ශ 𝐷∇ ⋅ 𝐸𝑑𝑉
ത Gauss theorem
1 1
ර 𝐷𝐸ത ∙ 𝑑 𝑠ҧ = 𝑞𝑖 = ශ 𝜌 𝑑𝑉 Gauss law
𝜀𝑜 𝜀𝑜
𝑖
𝜌
𝐷𝛻 ⋅ 𝐸ത =
𝜀𝑜
Chapter 21. The Electrostatic Potential
Poisson’s equation
Gauss divergence theorem
ර 𝑣ҧ ∙ 𝑑𝑠ҧ = ශ ∇ ⋅ 𝑣𝑑𝑉
ҧ 𝑣ҧ = 𝐷𝐸ത
ර 𝐷𝐸ത ∙ 𝑑 𝑠ҧ = ශ 𝐷∇ ⋅ 𝐸𝑑𝑉
ത Gauss theorem
1 1
ර 𝐷𝐸ത ∙ 𝑑 𝑠ҧ = 𝑞𝑖 = ශ 𝜌 𝑑𝑉 Gauss law
𝜀𝑜 𝜀𝑜
𝑖
𝜌
𝐷𝛻 ⋅ 𝐸ത = One of Maxwell’s equations
𝜀𝑜
Chapter 21. The Electrostatic Potential
Poisson’s equation
𝜌 combine with 𝐸ത = −∇𝜓
𝐷𝛻 ⋅ 𝐸ത =
𝜀𝑜
𝜌
𝛻2𝜓 = − 𝛻 2 Laplacian operator
𝐷𝜀𝑜
Chapter 21. The Electrostatic Potential
Image charges
Chapter 21. The Electrostatic Potential
Image charges
Chapter 21. The Electrostatic Potential
Image charges
𝐷𝑖𝑛 − 𝐷𝑜𝑡ℎ𝑒𝑟
𝑞′ = 𝑞
𝐷𝑖𝑛 + 𝐷𝑜𝑡ℎ𝑒𝑟
∁𝑞′
𝜓=
𝐷𝑖𝑛 2𝑑
