welcome to the chem 373 sixth edition + lab manual it is all on the web !!
TRANSCRIPT
Welcome to the Chem 373
Sixth Edition
+ Lab Manual
http://www.cobalt.chem.ucalgary.ca/ziegler/Lec.chm373/index.html
It is all on the web !!
Lecture 1: Classical Mechanics and the Schrödinger Equation
This lecture covers the following parts of Atkins 1. Further information 4. Classical mechanics (pp 911- 914 )2. 11.3 The Schrödinger Equation (pp 294)
Lecture-on-line Introduction to Classical mechanics and the Schrödinger equation (PowerPoint) Introduction to Classical mechanics and the Schrödinger equation (PDF)
Handout.Lecture1 (PDF) Taylor Expansion (MS-WORD)
Tutorials on-line The postulates of quantum mechanics (This is the writeup for Dry-lab-II)( This lecture has covered (briefly) postulates 1-2)(You are not expected to understand even postulates 1 and 2 fully after this lecture) The Development of Classical Mechanics Experimental Background for Quantum mecahnics Early Development of Quantum mechanics The Schrödinger Equation The Time Independent Schrödinger Equation
Audio-Visuals on-line Quantum mechanics as the foundation of Chemistry (quick time movie ****, 6 MB)Why Quantum Mechanics (quick time movie from the Wilson page ****, 16 MB) Why Quantum Mechanics (PowerPoint version without animations) Slides from the text book (From the CD included in Atkins ,**)
Classical Mechanics
A particle in 3-D has the following attributes
X
Y
Z
1. Mass m
m
mass
r r
Posit ion 2. Position
r r
r v = d
r r /dt
velocity
3. Velocity r v
Rate of change of position with time
Expression for total energy
ET =Ekin+Epot(r r )
The total energy of a particle with position
r r ,
mass m and velocity r v also has energy
Kinetic energy dueto motion
Potential energy due to forces
v p
v v small mass large velocity
v v
large mass small velocity
or
Linear Momentum and Kinetic Energy
Ek =12
mv2
The kinetic energy can be written as :
r p =m v v
Or alternatively in terms of the linear momentum:
as:
Ek =p2
2m
A particle moving in a potential energy field V is subject to a force
V(x)
X
F=-dV/dx
Force in one dimension
Force in direction of decreasing potential energy
The potential energy and force
v F =−dV
dxw e x−
dVdy
w e yPotential energy V
The force has the direction of steepest descend
Force F
The expression for the total energy in terms of the potential energy and the kinetic energy given in terms of the linear momentum
The Hamiltonian will take on a special importance in the transformation from classical physics to quantum mechanics
E =Ekin + Epot=
p2
2m+V(
r r )
is called the Hamiltonian
H =
p2
2m+V(
r r )
The Classical Hamiltonian
Quantum Mechanics
The particle is moving in the potential V(x,y,z)
Classical HamiltonianWe consider a particle of mass m,
Linear momentum
r p =m
r v
and positionr r
r r
r p =
X
Y
Z m
Positionmass
mv r
Linear Momentum
Classical Hamiltonian
r r
r p =
X
Y
Z m
Positionmass
mv r
Linear Momentum
The classical Hamiltonian is given by
H =12m
px2 + py
2 + pz2( ) +V(x,y,z)
H =
12m
r p⋅ r p +V( v r ) = 1
2mp2 +V( v r)
Quantum Mechanical Hamiltonian
The quantum mechanical Hamiltonian ˆ H is constructed by thefollowing transformations :
HClass → ˆ H =12m
ˆ px2 + ˆ py
2 + ˆ pz2( ) +V( ˆ x, ˆ y, ˆ z)
Classical Mechanics Quantum Mechanics
x px ˆ x −> x ; ̂ px−>hiδδx
y py ˆ y−> y ; ̂ py−>hiδδy
z pz ˆ z−> z ; ̂ pz−>hiδδz
Here h ' h - bar'=
h2π
is a modification of Plancks constanth
h=1.05457 × 10−34 Js
ˆ H =12m
( ˆ px2 + ˆ py
2 + ˆ pz2) +V( ˆ x, ˆ y, ˆ z)
= 12m
[(hiδδx
×hiδδx
) + (hiδδy
×hiδδy
) + (hiδδz
×hiδδz)] +V(x,y, z)
We have
hiδδy
×hiδδy
=h2
i2δδy
×δδy
=−h2δ2
δy2
Thus
ˆ H =−
h2
2m[δ2
δx2 +δ2
δy2 +δ2
δz2]+V(x,y,z)
By introducing the Laplacian : ∇2 =δ2
δx2+
δ2
δy2+
δ2
δz2 we have
ˆ H =−h2m
∇2 +V(x, y, z)
It is now a postulate of quantum mechanics that :
the solutions Ψ(x, y, z) to the Schrödinger equation
ˆ H Ψ(x, y, z)=EΨ(x, y, z)
−h2
2m∇2Ψ(
r r ) +V( r r )Ψ(
r r) =EΨ( r r)
−h2
2m[δ2Ψδx2
+δ2Ψδy2
+δ2Ψδy2
] +V(x,y,z)Ψ =EΨ
Contains all kinetic information about a particle moving in the Potential V(x,y,z)
ˆ H =−
h2
2m[δ2
δx2 +δ2
δy2 +δ2
δz2]+V(x,y,z)
What you should learn from this lecture
Definition of :
Linear momentum (pm),
kinetic energy(p2
2m);
Potential Energy
Relation between force F
and potential energy V (r F =-
r ∇ V)
The definition of the Hamiltonian (H)
as the sum of kinetic and potential energy,
with the potential energy written in terms
of the linear momentum
For single particle: H=
p2
2m+V(
r r )
You must know that :The quantum mechanical Hamiltonian ˆ H is constructed from the classical Hamiltonian H by the transformation
HClass → ˆ H =12m
ˆ px2 + ˆ py
2 + ˆ pz2( ) +V( ˆ x, ˆ y, ˆ z)
Classical Mechanics Quantum Mechanics
x px ˆ x −> x ; ̂ px−>hiδδx
y py ˆ y−> y ; ̂ py−>hiδδy
z pz ˆ z−> z ; ̂ pz−>hiδδz
The position of the particle is a function of time.
Let us assume that the particle at t =tohas the position
r r (to )
and the velocity r v (to ) =(d
r r /dt)t=to
What is v r (to +Δ )t = v r(t1)= ?
v r (to +Δt)=
v r (to)+(d
v r /dt)t=to Δt+
12
(d2v r /dt2)t=to Δt2
v r (to +Δt)=
v r (to)+
v v (to)Δt+
12
(d2v r /dt2)t=to Δt2
By Taylor expansion around r r (to )
or
Newton's Equation and determination of position..cont
v r (t o )
v r (to
+Δt)
(d2 v r / dt2 )t=to
Δt2 (d
v r / dt )t=toΔt
Appendix A
v r (t o )
v r (to
+Δt)
v v (t o )Δ t (d
2v r / dt2 )t=toΔt2
v r (to +Δt)=
v r (to)+
v v (to)Δt+
12
(d2v r /dt2)t=to Δt2
v F (to ) =−
v∇ V =−gradV=m(d2 v r /dt2 )t=to
However from Newtons law:
v r (to +Δt)=
v r (to)+
v v (to)Δt-
12m
(gradV)t=t0Δt2Thus :
Newton's Equation and determination of position..contAppendix A
v r (t o )
v r (to
+Δt) v v (to)Δt
- 1m(gradV)
t=toΔt
v r (to +Δt)=
v r (to)+
v v (to)Δt-
12m
(gradV)t=t0Δt2
Newton's Equation and determination of position..cont
At the later time : t1 =to +Δt we have
v r (t1+Δt)=
v r (t1)+(d
v r /dt)t=t1Δt+
12(d2v
r /dt2)t=t1Δt2(1)
The last term on the right hand side of eq(1) can again be determined from Newtons equation
v F (t1 ) =−
v∇ V =−gradV=m(d2 v r /dt2 )t=t1
as
(d2v r / dt2 )t=t1 =−
1m(gradV)t=t1
Newton's Equation and determination of position..cont
Appendix A
We can determine the first term on the right side of eq(1) By a Taylor expansion of the velocity
v r (t1+Δt)=
v r (t1)+(d
v r /dt)t=t1Δt+
12m
(gradV)t=t1Δt2(1)
(d
v r /dt)t=t1 =(d
v r /dt)t=t0 +
12(d2v
r /dt2)t=t0Δtor
(d
v r /dt)t=t1 =v v (to)−
12m
(gradV)t=toΔt
Where both: v v (to ) and
1m
(gradV)t=to are known
Newton's Equation and determination of position..contAppendix A
The position of a particle is determined at all times from the position and velocity at to
v v (t2)=(d
v r /dt)t=t2 =v v (t1)−
1m
(gradV)t=t1Δt
Newton's Equation and determination of position..cont
v r (t2+Δt)=
v r (t2)+
v v (t2)Δt+12(d2v
r /dt2)t=t2Δt2
(d2v
r /dt2)t=t2 =−1m
(gradV)t=t2
At t2 =t0 +2Δt what about v r (t2+Δt) ?
v r (t2 )
v r (t2 +Δt)
v v (t2 )Δt
- 1m(gradV)
t= t 2
Δ t
Appendix A