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Schrödinger Equation, Operators, Etc

The document discusses key concepts related to the Schrödinger equation including: 1) The state of a quantum system is defined by a wavefunction ψ that contains all information about the system. 2) Operators like position x, momentum p, and kinetic energy K act on wavefunctions according to mathematical relationships. 3) Wavefunctions must satisfy conditions like being single-valued, continuous, and normalizable over all space for a physical system.

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45 views22 pages

Schrödinger Equation, Operators, Etc

The document discusses key concepts related to the Schrödinger equation including: 1) The state of a quantum system is defined by a wavefunction ψ that contains all information about the system. 2) Operators like position x, momentum p, and kinetic energy K act on wavefunctions according to mathematical relationships. 3) Wavefunctions must satisfy conditions like being single-valued, continuous, and normalizable over all space for a physical system.

Uploaded by

JM
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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1.22.

2019
Schrödinger equation, operators, etc.
Schrödinger equation
• The state of a system is defined by a function, ψ.
• All the information that can be known about the system is embedded
in the function.
• The system can be a single electron, an atom, a group of atoms, or
whatever we can write a sufficiently detailed version of ψ for.
Coordinates
• A critical part of how we describe our system is the coordinate system
• Cartesian
• Spherical Polar
• Any set of orthogonal coordinates that fit the problem
Physical significance of state function
• The significance of the state function is that Ψ∗ Ψ serves as a
probability distribution function.
• Ψ∗ Ψdxdydz= Ψ 2
• The state function expressed this way is indicative of the likelihood
that we will find the particle in the region x to (x + dx), y to (y + dy), z
to (z + dz)
Conditions for a State Function
• Single valued. At any position (x,y,z), Ψ 2 can have only one
numerical value
• The state function and first and second derivatives of the state
function must be finite and continuous at all points.
• The function Ψ 2 must have a finite integral over all space
Phase of a wavefunction
Normalization
• We have a normalized state function when we generate a Ψ such that
+∞ ∗
• ‫׬‬−∞ Ψ Ψ𝑑τ =1
• We don’t have to generate a normalized wavefunction, but our lives
are easier if we do.
Electron bound in a region of length ’L’
2𝜋𝑥
• 𝜓 = sin
𝐿
𝐿 2𝜋𝑥 2𝜋𝑥
• ‫׬‬0 nsin 𝐿 nsin 𝐿 𝑑𝑥 =1
2 𝐿 2 2𝜋𝑥
• 𝑛 ‫׬‬0 𝑠𝑖𝑛 𝑑𝑥 = 1
𝐿
2 1
• ‫ = 𝑥𝑑 𝑥 𝑛𝑖𝑠 ׬‬2 [𝑥 − sin 𝑥 cos 𝑥 ]
• Solve for ‘n’ the normalization constant
Wavefunction Normalization
Fundamental Operators
• 𝑥ො
• 𝑦ො
• 𝑧Ƹ
ħ 𝜕
• 𝑝Ƹ𝑥 =
𝑖 𝜕𝑥
ħ 𝜕
• 𝑝Ƹ𝑦 =
𝑖 𝜕𝑦
ħ 𝜕
• 𝑝Ƹ𝑧 =
𝑖 𝜕𝑧
Operator Relationships
• Additional operators can be constructed from the fundamental
operators
Eigenvalue Relationship

•𝛼𝑓
ො 𝑥 = 𝑎𝑓(𝑥)
𝑘𝑥
𝑓 𝑥 = 𝑐𝑒
• All functions of this form are eigenfunctions of the 𝑑መ operator.
• ‘k’ and ‘c’ are constants, and the eigenvalue is ‘k’
Basis Sets
• ψ = σ∞
𝑖=1 𝑐𝑖 𝑥𝑖
Orthogonality
• ‫ = 𝜏𝑑 𝑗𝜓 ∗𝑖𝜓 ׬‬0 𝑤ℎ𝑒𝑛 𝑖 ≠ 𝑗

B
Operators
• Commutators
መ 𝐵෠ = 𝐴መ 𝐵෠ − 𝐵෠ 𝐴መ
• 𝐴,
መ 𝐵෠ = 0, the operators are said to commute
• If 𝐴,
መ 𝐵෠ ≠ 0, we say that the operators do not commute
• If 𝐴,
• For any function f, we can write
መ 𝐵෠ 𝑓 = 𝐴መ 𝐵𝑓
• 𝐴, መ
෠ − 𝐵෠ 𝐴𝑓
Kinetic Energy, Momentum, Position
ℏ2 𝜕
෡=
•𝐾 −
2𝑚 𝜕𝑥 2

𝜕
• 𝑝Ƹ = −𝑖ℏ
𝜕𝑥

• Do these operators commute?

• Do 𝑝Ƹ and 𝑥ො commute?
Quantum Average Value Theorum
መ 𝑑𝜏
• 𝐴 = ‫𝜓𝐴 ∗ 𝜓 ׬‬
Schrödinger Equation – Experiment/Theory
Particle in a 1-d box

∞ ∞

0 a

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