Quantum Mechanics
Table of Contents
1. Formalism
1.1. Hilbert Space
Set of all possible quantum states \(\ket{\psi}\) is postulated to form a Hilbert space \(\mathcal{H}\).
The state space \(\mathcal{H}\) of many-aspect system is the tensor product of the state spaces of each aspect \(\mathcal{H}_i\). \[ \mathcal{H} = \bigotimes_i\mathcal{H}_i. \]
1.2. Operator
It is postulated that for every observable \(Q\) there exists hermitian operator \(\hat{Q}\) such that: \[ \ev{Q} = \mel{\psi}{\hat{Q}}{\psi}. \] furthermore, for eigenstates \(\ket{Q_i}\), \[ Q_i\ket{Q_i} = \hat{Q} \ket{Q_i}. \]
1.2.1. Momentum Operator
Momentum operator \(\hat{\mathbf{p}}\) is the generator of translation \(\hat{U}(\mathbf{x})\): \[ \hat{U}(\mathbf{x}) = e^{-i\hat{\mathbf{p}}\vdot \mathbf{x}/\hbar}. \]
\begin{align*} \grad \hat{U}(\mathbf{x})\ket{\mathbf{x}} &= \left( \frac{\hat{U}(\dd{\mathbf{x}}) - \hat{U}(\mathbf{0})}{\dd{\mathbf{x}}} \right)\ket{\mathbf{x}} \\ &= \frac{\ket{\mathbf{x} + \dd{\mathbf{x}}} - \ket{\mathbf{x}}}{\dd{\mathbf{x}}} \\ &= \pdv{\mathbf{x}} \ket{\mathbf{x}} \\ &= \frac{1}{i\hbar} \hat{\mathbf{p}} \ket{\mathbf{x}}. \end{align*}The position basis form of momentum operator is derived as follows:
\begin{align*} \mel{\mathbf{x}}{\hat{\mathbf{p}}}{\psi} &= \bra{\mathbf{x}} \int_{\Omega} \dd[3]{\mathbf{x}'} \psi(\mathbf{x}')\hat{\mathbf{p}}\ket{\mathbf{x}'} \\ &= \bra{\mathbf{x}} \int_{\Omega} \dd[3]{\mathbf{x}'} \psi(\mathbf{x}')i\hbar \pdv{\mathbf{x}'}\ket{\mathbf{x}'} \\ &= \bra{\mathbf{x}} \int_{\Omega} \dd[3]{\mathbf{x}'}i\hbar \pdv{\mathbf{x}'}\left( \psi(\mathbf{x}')\ket{\mathbf{x}'} \right) + \bra{\mathbf{x}} \int_{\Omega} \dd[3]{\mathbf{x}'} \left( - i\hbar \pdv{\mathbf{x}'}\psi(\mathbf{x}') \right)\ket{\mathbf{x}'}\\ &= \bra{\mathbf{x}}\oint_{\partial \Omega}\dd[2]{\mathbf{x}'}i\hbar \psi(\mathbf{x}')\ket{\mathbf{x}'} + \bra{\mathbf{x}} \int_{\Omega} \dd[3]{\mathbf{x}'} \left( - i\hbar \pdv{\mathbf{x}'}\psi(\mathbf{x}') \right)\ket{\mathbf{x}'} \\ &= \bra{\mathbf{x}} \int_{\Omega} \dd[3]{\mathbf{x}'} \left( - i\hbar \pdv{\mathbf{x}'}\psi(\mathbf{x}') \right)\ket{\mathbf{x}'} \\ &= \int_{\Omega} \dd[3]{\mathbf{x}'} \left( - i\hbar \pdv{\mathbf{x}'}\psi(\mathbf{x}') \right)\delta^3(\mathbf{x} - \mathbf{x}') \\ &= -i\hbar \pdv{\mathbf{x}} \psi(\mathbf{x}) \end{align*}where the wave function \(\psi(\mathbf{x})\) is assumed to be localized and the boundary term vanishes.
1.2.2. Lie Theory
The unitary operators \(\hat{U}\) form a Lie group, and the Hermitian operators \(\hat{H}\) are related to the Lie algebra that generate that Lie group by the exponential map: \[ \exp\colon \frac{1}{i\hbar}\hat{H} \mapsto \hat{U}. \]
Hermitian operator of an observable \(p\) maps to transformation in its conjugate variable \(q\). The justification comes from the quantum equivalent of Hamilton's equations:
\begin{align*} &\pdv{q}\ev{H} = - \dv{t} \ev{p} \\ \implies &\pdv{\bra{\psi}}{q} \hat{H}\ket{\psi} + \bra{\psi} \pdv{\hat{H}}{q}\ket{\psi} + \bra{\psi}\hat{H} \pdv{\ket{\psi}}{q}= - \left(\dv{\bra{\psi}}{t} \hat{p}\ket{\psi} + \bra{\psi} \dv{\hat{p}}{t}\ket{\psi} + \bra{\psi}\hat{p} \dv{\ket{\psi}}{t}\right). \end{align*}Let us assume that the Hamiltonian operator does not explicitly depend on \(q\) (not \(\hat{q}\)), and canonical momentum operator \(\hat{p}\) does not explicitly depend on time. Using Schrödinger Equation, the equation becomes:
\begin{align*} \pdv{\bra{\psi}}{q} \hat{H}\ket{\psi} + &\bra{\psi}\hat{H} \pdv{\ket{\psi}}{q} \\ = \mel{\psi}{-\frac{1}{i\hbar}\hat{p}\hat{H}}{\psi} + &\mel{\psi}{\hat{H}\frac{1}{i\hbar}\hat{p}}{\psi}. \end{align*}This strongly suggests the following identity \[ i\hbar \pdv{q} \ket{\psi} = \hat{p} \ket{\psi} \] and consequently the generator relation: \[ \hat{U}(q) = \exp(\frac{\hat{p} q}{i\hbar}). \] where \(\hat{U}(q)\) is the translation operator in the general coordinate \(q\) by \(q\) amount.
Similar argument can be made for the second Hamilton equation. From \[ \pdv{p}\ev{H} = \dv{t}\ev{q}, \] we get: \[ -i\hbar \pdv{p}\ket{\psi} = \hat{q}\ket{\psi} \] and \[ \hat{U}(p) = \exp(-\frac{\hat{q}p}{i\hbar}) \]
1.3. Canonical Commutation Relation
\[ \frac{1}{i\hbar}[\hat{\mathbf{x}}, \hat{\mathbf{p}}] = \mathbf{1}. \]
It is easy to show from the assumption that momentum is the generator of spatial translation: \[ \ev{\left[\hat{\mathbf{x}}, \frac{1}{i\hbar}\hat{\mathbf{p}}\right]} = \pdv{\ev{x}}{x} = 1. \]
1.4. Uncertainty Relation
- Uncertainty Principle
This answers why the electron doesn't fall to the nucleus. Quantum particles cannot be localized, because of quantum fuzziness. By uncertainty principle, if a particle happens to be localized, then it would have very high momentum for the particle to fly away.
2. Schrödinger Equation
Quantum equivalent of Hamilton's equations.
The basis-independent equation is given by: \[ i\hbar \pdv{t} \ket{\psi} = \hat{H}|\psi\rangle \] where \(\hat{H}\) is the hamiltonian operator, and \(\ket{\psi}\) is the state vector.
The solution to this equation can be given simply as: \[ \ket{\psi(t)} = e^{-i\hat{H}t/\hbar} \ket{\psi_0}. \]
2.1. Basis-dependent Equations
Position-basis Equation \[ i\hbar \pdv{t}\psi(\mathbf{x}) = \mel{\mathbf{x}}{\hat{H}}{\psi} \]
For a simple Hamiltonian of the form \(H = T + V\), \[ i\hbar \pdv{t}\psi(\mathbf{x}) = -\frac{\hbar^2}{2m}\laplacian\psi(\mathbf{x}) + V(\mathbf{x})\psi(\mathbf{x}) \]
Momentum-basis Equation \[ i\hbar \pdv{t}\phi(p) = \mel{p}{\hat{H}}{\psi} \]
For simple Hamiltonian of the form \(H = T + V\), \[ i\hbar \pdv{t} \phi(p) = \frac{p^2}{2m}\phi(p) + V \left( i\hbar \pdv{p} \right)\phi(p). \]
Energy-basis Equation \[ i\hbar \pdv{t}c(E) = \mel{E}{\hat{H}}{\psi} \]
For simple Hamiltonian of the form \(H = T + V\), \[ i\hbar \pdv{t} c(E) = E c(E). \]
2.2. Time-Independent Schrödinger Equation
When \(\psi\) is of the form \(\psi(\mathbf{x})e^{-iEt/\hbar}\) , we have \[ \hat{H}\psi = E\psi \] where \(\psi(\mathbf{x})e^{-iEt/\hbar}\) is called the energy eigenstate.
2.3. For Hydrogen Atom
The potential energy operator is given by the electrostatic potential energy: \[ \hat{V} = -\frac{e^2}{4\pi\varepsilon_0\hat{r}}. \]
The solution can be obtained using the separation of variable technique in spherical coordinates: \[ \psi=R_{n,l}(r)Y_l^m(\theta, \phi)e^{-iEt/\hbar} \] where \(R_{n,l}(r)\) is radial function, \(Y_l^m(\theta, \phi)\) is sperical harmonics.
2.3.1. Radial Function
- Starts positive at \(r=0\) , flips sign \(n-l-1\) times.
- flattens as \(n\) gets large.
2.3.2. Sperical Harmonics
- basis function for all sperical functions.
- smooth at every points.
- it is the orbitals in chemistry when the real part of the function is taken.
- it flips its phase \(l-|m|\) times, when going from north pole to the south.
- it rotates in phase \(m\) times, as circling along the azimuthal plane.
3. Heisenberg Picture
The state vector does not change, but the operator itself changes over time.
3.1. Heisenberg's Equation
- Heisenberg Equation of Motion
\[ \dv{t} A_{\rm H}(t) = \frac{1}{i\hbar} [A_{\rm H}(t), H_{\rm H}(t)] + \left( \dv{A_{\rm S}}{t} \right)_{\rm H} \] where \(A_{\rm S}\) is the operator in Schrödinger picture, and subscript \(\rm H\) makes it into an operator in Heisenberg picture again.
Partial derivative notation is usually prefered for \(A_{\rm S}\) to emphasize the derivative is taken with respect to the explicit dependence on time of the operator. However, from mathematical point of view there is no reason to use it. I find it more confusing to use partial derivative, and I chose to stick to the mathematical convention.
4. Density Matrix
It can contain both quantum and statistical uncertainties For pure state \(\ket{\psi}\):
- \[ \rho = \ket{\psi}\bra{\psi} \]
- idempotent: \(\rho = \rho^2\)
- purity of one: \(\tr \rho^2 = 1\)
For mixed state:
- \[ \rho = \sum_j p_j \ket{\psi_j}\bra{\psi_j}\]
The expectation value can be calculated: \[ \expval{A} = \tr(\rho A). \]
4.1. Von Neumann Equation
- Liouville-von Neumann equation
\[ i\hbar \dv{t}\rho = [H, \rho]. \]
5. Spinor
5.1. Pauli Spin Matrices
5.1.1. Definition
Sometimes the identity matrix is included as \(\sigma_0\).
5.1.2. Properties
- Hermitian, Involutory, Unitary.
- They, together with the identity matrix \(I = \sigma_0\), form the basis for the real vector space of \(2\times 2\) Hermitian matrices.
- Anti-Commutativity under Multiplication.
- It is the linear map (order 3 tensor) from the three dimensional
vector space \(V\) to the spinor-pair space \(S\otimes S^*\):
- \[ \sigma_i\vphantom{\sigma}^{a}\vphantom{\sigma}_b \]
- where \(a\) is the index for the spinor space \(S\) and \(b\) is the index for the dual spinor space \(S^*\).
- It is with respect to the standard spinor basis.
5.1.3. Interpretation
- It represents the interaction between the spin of a particle with an
external electromagnetic field, which is best represented in the
- \(\sigma s = s'\)
- It also represents the observables which are the Hermitian matrices.
- \(\langle s | \sigma | s \rangle\)
- It is equivalent to the three basis vector of the Clifford Algebra \(\mathrm{Cl}_{3,0}(\mathbb{R})\).
5.1.4. Infeld-Van der Waerden Symbols
\[ \sigma_\mu^{a\dot{b}} \]
- Generalization of the Pauli matrices to the four dimensional spacetime.
- Using the 5.5.3.1.
5.2. Pauli Vector
- Vectors with the basis of
\[ \begin{bmatrix}x\\ y \\ z \end{bmatrix} \rightsquigarrow \begin{bmatrix} z & x - yi \\ x+ yi & -z \end{bmatrix} = x\sigma_x + y\sigma_y + z\sigma_z \]
It is mostly equivalent to the three dimensional geometric algebra, with the exception that it admits s, since the components can be complex numbers.
5.2.1. Conjugation
Conjugation rotates \(\pi\) radians around the axis:
\begin{align*} \sigma_x &\rightsquigarrow \sigma_z\sigma_x\sigma_z^{-1} = \sigma_z\sigma_x\sigma_z = -\sigma_z\sigma_z\sigma_x = -\sigma_x \\ \sigma_y &\rightsquigarrow \sigma_z\sigma_y\sigma_z^{-1} = \sigma_z\sigma_y\sigma_z = -\sigma_z\sigma_z\sigma_y = -\sigma_y \\ \sigma_z &\rightsquigarrow \sigma_z\sigma_z\sigma_z^{-1} = \sigma_z\sigma_z\sigma_z = +\sigma_z \end{align*}- And negative conjugation by \(\sigma_z\) reflects along the \(z\) axis.
5.2.2. Reflection and Rotation
- Two reflections is a rotation.
- Pauli vectors are reflected by the Pauli matrices by the conjugation.
- And rotated by the two pairs of unit Pauli vectors, which are the members of the \(\mathrm{SU}(2)\) group.
- Using some abstract algebra, the \(\mathrm{SU}(2)\) matrices are all the matrix the rotates a Pauli vector, (up to a complex multiple, which does not matter what that is so the determinant is just taken to be 1).
5.2.3. Properties
- Traceless Hermitian Matrix
- It squares to the square magnitude of the vector.
- The determinant is the negative of the square magnitude.
- The sum of pairs of sigma matrices are equivalent to the quaternion.
- Both the group of unit quaternions and \(\mathrm{SU}(2)\) are isomorphic to the \(\mathrm{Spin}(3)\) Group, describing the spin in three dimensional space, which is the double cover of rotation group \(\mathrm{SO}(3)\).
5.3. Pauli Spinor
- See ,
- The factorization of the Pauli vectors into column and row spinors.
- "Square root of a Vector"
- A vector is linearly mapped to a Pauli vector which then can be factored.
- It multiplys to form a rank 1 tensor, hence it is a rank ½ tensor.
- The direct factorization is possible only when \(\det = 0\),
i.e. ((65c64b17-5672-4d8f-bb56-59bc3b907725)) 1.
\[
\begin{bmatrix} z & x-yi \\ x+yi & -z \end{bmatrix} = \begin{bmatrix} \sqrt{x-yi} \\ -i\sqrt{x+yi} \end{bmatrix} \begin{bmatrix} i\sqrt{x+yi} & \sqrt{x-yi} \end{bmatrix} =: \begin{bmatrix} \xi^1 \\ \xi^2 \end{bmatrix}\begin{bmatrix} -\xi^2 & \xi^1 \end{bmatrix}\]
- When the rank is greater than 1, the matrix can be written as the sum of product of spinors.
5.3.1. Rotation
- It is rotated by a single \(\mathrm{SU}(2)\) matrix, which is half of the rotation of the Pauli vector, that does not change the length of the spinor: \[ \lVert U\xi \rVert^2 = (U\xi)^\dagger (U\xi) = \xi^\dagger U^\dagger U\xi = \xi^\dagger \xi = \lVert \xi \rVert^2. \]
- The spinors on the Poincaré sphere and the Bloch sphere is also rotated in the same way.
5.4. Weyl Vector
- Using the :
- \[ ct\sigma_t + x\sigma_x + y\sigma_y + z\sigma_z = \begin{bmatrix} ct + z & x-yi \\ x+yi & ct-z \end{bmatrix} \]
- with \(\sigma_t\) being the identity matrix.
5.4.1. Properties
- Hermitian matrix
- The determinant is the spacetime interval.
- It transforms with \(\mathrm{SL}(2, \mathbb{C})\) matrices.
- The transformation matrix is special and Hermitian
- The boosts uses the hyperbolic functions
5.5. Weyl Spinor
- Spinor in four dimensional spacetime.
Weyl vector can be factored into Weyl spinors
\begin{bmatrix} ct + z & x-yi \\ x+yi & ct-z \end{bmatrix} = \begin{bmatrix} \psi^1 \\ \psi^2\end{bmatrix}\begin{bmatrix} {\psi^1}^* & {\psi^2}^*\end{bmatrix} = \begin{bmatrix} \psi^1 \\ \psi^2\end{bmatrix}\begin{bmatrix} \psi^{\dot{1}}& \psi^{\dot{2}}\end{bmatrix}with \(|\psi^1| = \sqrt{ct+z}, |\psi^2| = \sqrt{ct-z}\) and the phase difference \(\theta_2 - \theta_1 = \arctan(y/x)\).
5.5.1. Inner Product
- \(\psi^\dagger \epsilon \phi\) is never conserved.
- So \(\psi^\top \epsilon \phi\) is chosen as the inner product with
- \[ \epsilon = \begin{bmatrix} 0 & 1 \\ -1 & 0\end{bmatrix}. \]
- It is alternating.
- \(\epsilon\) is called a
5.5.2. Dual Spinor
- From the inner product
\[ \psi^\top\epsilon \]
- The complex conjugate of a left spinor \(\psi\) becomes the right dual spinor \(\psi^*\).
- The right spinor would be \(\psi^\dagger \epsilon\).
5.5.3. Chirality
- It has left and right chirality, which is notated by \(\psi^a, \psi_a\) and \(\psi^{\dot{a}}, \psi_{\dot{a}}\).
- This happens because the \(\mathrm{SO}(2,\mathbb{C})\) has two
different representation, left and right. The two are connected by
complex conjugation.
- Unlike \(\mathrm{SU}(2)\), there is no invertible matrix \(P\), such that \(L^* = P^{-1}LP\).
5.5.3.1. Van der Waerden Notation
- Placing dot above the right chiral spinor indices.
5.6. Dirac Spinor
- The spinor in the four dimensional spacetime, that accounts for the .
- It consists of a left chiral Weyl spinor and a right chiral Weyl spinor.
5.7. Spin Group
- The double cover of \(\mathrm{SO}(n)\) is called the spin group
\(\mathrm{Spin}(n)\).
- It is the group of generalization of unit quaternions for \(n\)-dimensional space.
- The double cover of \(\mathrm{SO}^+(p,q)\) is called the spin group \(\mathrm{Spin}(p,q)\).
- The systematic construction of spin groups involves the use of .
6. Wigner Quasipropability Distribution
- Wigner function, Wigner-Ville distribution
- The "probability" over phase space
\[ W(x,p) := \frac{1}{\pi \hbar} \int_{-\infty}^{\infty} \psi^{*}(x+y) \psi(x-y) e^{2ipy/\hbar} \dd{y} \]
Short-term Fourier transform with itself as the weight function.