Group Presentation

Quantum Tunnelling
 What is Quantum Tunnelling ?

E<V E>V
(Reflect)
 Classical mechanics:
Particle with
If the particle has energy E less than the
Energy E
potential energy barrier (V), then it will
not get over the barrier.

Potential Energy
Barrier (V)

 If the quantum particle has energy E

less than the potential energy barrier V,
there is still a probability of finding
Quantum Particle(like electron)
the particle on the right region !
with Energy E
This phenomenon is called
Quantum tunneling.
E<V
 Quantum Tunneling : Let us understand

History
 First used to explain alpha decay of heavier elements in 1928 by George Gamow.
 Shown experimentally by Leona Esaki in 1958 in the tunneling diode.

Quantum Mechanics
 In the quantum mechanics, matter has corpuscular and wave-like properties

 Quantum Mechanics is Probabilistic

 The Heisenberg Uncertainty principle
Instead of a Particle Now consider a wave

Wave function High Probability

Low Probability Potential barrier

Total Internal
Reflection
Take an example Reflection
of light (an EM
wave) Light beam Light beam

100% Reflection
MAYBE NOT
Refraction
By solving Maxwell equation at the
boundary
Evanescent wave: It Decays very quickly
 There is a small probability that electron is present here

If the barrier is thin enough the waves do not decay completely

Energy the electron

is allowed to have

Wave function
Kinetic Energy Potential Energy
Schrodinger wave equation
 Newtonian Mechanics for
position of a ball

Quantum Mechanics for

position of a particle  Energy level
somewhere in a box  Wave function

Particle in a Box
What this actually means ?

Probability of
finding the electron 20%
in the box at a 5% 10%
certain position
15%
12%

6%

Probability distribution
This means that the electron must lie inside the box only and
spread out over a large
cannot be found outside the box
space like a wave! Hence
we need wave function
Energy levels of electron are also required .
Particle in a box actually is ?

Infinite potential well: Barriers

are of infinite height and width

If the walls are thin enough there

is a small probability of finding
an electron outside the box.
Hence the term tunnelling.
Transition state theory for enzyme kinetic isotope effects
KB = Boltzmann constant
h = Plank constant

𝑘𝐵 𝑇 𝑄 ∗ 𝜀∗ R = Gas constant
− Q* = transition state partition function
𝐾 𝑇 =𝑘 x 𝑅𝑒 𝑅𝑇 QR = Reactant state partition function
ℎ 𝑄 ĸ = transmission coefficient for
quantum tunnelling

R1,R2 = enzyme substrate conformers

P = enzyme substrate product complex
Kf ,kr = forward and backward inter-
conversion between R1 and R2
Keq = Kf / Kr
 [R’] = [R1 + R2] 𝑅′ −𝑑[𝑅′ ] −𝑑( 𝑅1 + 𝑅2 )
𝑅1 = = = 𝑘 ′ [𝑅′ ]
1 + 𝐾𝑒𝑞 𝑑𝑡 𝑑𝑡
Concentration
R1 and R2 𝑅′ 𝐾1 𝐾2 ′
𝑅2 = = + [𝑅 ]
1 + (𝐾𝑒𝑞 )−1 1 + 𝐾𝑒𝑞 1 + (𝐾𝑒𝑞 ) −1

For H and D
Where −𝜀1𝐻 /𝑅𝑇
𝐾1𝐻 = 𝑘1𝐻 (𝑇)𝐶1 𝑇𝑒 𝐾1𝐻 𝐾2𝐻
−𝜀2𝐻 /𝑅𝑇 𝐾𝐻′ = +
𝑘𝐵 𝑄𝑖𝑇𝑆 𝐾2𝐻 = 𝑘2𝐻 (𝑇)𝐶2 𝑇𝑒 ∆𝐺
(−𝑅𝑇)
∆𝐺
(𝑅𝑇 )
𝐶𝑖 ≈ 1 +𝑒 1+𝑒
ℎ 𝑄𝑖𝑅 𝐾1𝐷 𝐾2𝐷
𝐾1𝐷 = 𝑘1𝐷 (𝑇)𝐶1 𝑇𝑒 −𝜀1𝐷 /𝑅𝑇
𝐶1 and 𝐶2 are isotopometric
𝐾𝐷′ = ∆𝐺
+ ∆𝐺
(−𝑅𝑇) (𝑅𝑇)
rate constants 𝐾2𝐷 = 𝑘2𝐷 (𝑇)𝐶2 𝑇𝑒 −𝜀2𝐷 /𝑅𝑇 1 +𝑒 1+𝑒

𝛽 Where ∆𝐺 = −𝑅𝑇𝑙𝑛(𝐾𝑒𝑞 )
𝑙 𝛽−𝛼𝑖𝑙 𝑉𝑙𝑇𝑆
𝑘𝑖 T ≈ 𝑙 [𝑒 − 1] K(T)= Thermally averaged transmission coefficient for
𝛽 − 𝛼𝑖 quantum tunnelling β = [(kT) –1] ,
𝛼𝑖𝑙 is Transition state imaginary frequency 𝑉𝑙𝑇𝑆 is Classical Transition State Energy
𝛼𝑖𝑙 = 2𝜋/(ℎ𝜔𝑖𝑙 ) 𝜔𝑖𝑙 is magnitude of corresponding Transition l is isotop index (H or D) and i is corresponding conformer
state imaginary frequency number (1, 2 …)
𝐾1𝐻 = 𝑘1𝐻 (𝑇)𝐶1 𝑇𝑒 −𝜀1𝐻 /𝑅𝑇 • soybean lipoxygenase (SLO-1),
• aromatic amine dehydrogenase (AADH),
−𝜀2𝐻 /𝑅𝑇 Where 𝑘𝐵 𝑄𝑖𝑇𝑆 • methylamine dehydrogenase (MADH)
𝐾2𝐻 = 𝑘2𝐻 (𝑇)𝐶2 𝑇𝑒 𝐶𝑖 ≈ • dihydrofolate reductase (DHFR)
ℎ 𝑄𝑖𝑅
−𝜀1𝐷 /𝑅𝑇
𝐾1𝐷 = 𝑘1𝐷 (𝑇)𝐶1 𝑇𝑒
𝐶1 and 𝐶2 are isotopometric
−𝜀2𝐷 /𝑅𝑇
𝐾2𝐷 = 𝑘2𝐷 (𝑇)𝐶2 𝑇𝑒 rate constants

lnK (S-1)
𝛽 𝛽−𝛼𝑖𝑙 𝑉𝑙𝑇𝑆
𝑘𝑖𝑙 T ≈ 𝑙 [𝑒 − 1]
𝛽 − 𝛼𝑖

1000/T
𝛼𝑖𝑙 = 2𝜋/(ℎ𝜔𝑖𝑙 )
𝑄𝑖𝑇𝑆
C1 and C2 followed by
KH/KD

𝑄𝑖𝑅

𝜀1𝐻 ≤ 𝜀1𝐷 , 𝜀2𝐻 ≤ 𝜀2𝐷 𝜀1𝐻 , 𝜀2𝐻 , 𝜀1𝐷 , 𝜀2𝐷

Assumption
𝑘1𝐻 (𝑇)= 𝑘1𝐷 (𝑇)=1 To analyse C-H and C-D
dissociation
1000/T