[QMSE] W02 - schrödinger’s Wave Equation
- used to solve problems for quantum mechanical particles that have mass
- single electron moving slowly (much slower than the velocity of light), neglecting magnetic effects
- exposes general concepts that come up repeatedly in quantum mechanics
- underlying linearity of quantum mechanics
- quantum mechanical amplitudes
- eigenstates (quantum aspect of quantum mechanics)
from de broglie to schrödinger
electron as waves
- de Broglie’s hypothesis is that the electron wavelength \( \lambda \) is given by
- \( \lambda = \frac{h}{p} \)
- where
- \( p \) is the electron momentum
- \( h \) is Planck’s constant
- \( h = 6.626… \times 10^{-34} Js \)
helmholtz’s wave equation to schrödinger
- considering only waves of one wavelength \( \lambda \) (i.e. monochromatic waves)
- \( \frac{d^2 \psi}{d z^2} = -k^2\psi \)
- \( k = \frac{2\pi}{\lambda} \)
- has solutions of the form:
- \( \sin(kz), \cos(kz), \exp(ikz) \)
- \( \sin(-kz), \cos(-kz), \exp(-ikz) \)
- \( \frac{d^2 \psi}{d z^2} = -k^2\psi \)
- in 3D, we can write this as
- \( \nabla^2 \psi = \frac{\partial^2 \psi}{\partial x^2} + \frac{\partial^2 \psi}{\partial x^2} + \frac{\partial^2 \psi}{\partial x^2} = -k^2\psi \)
- which has solutions like
- \( \sin(\textbf{k}\cdot\textbf{r}), \cos(\textbf{k}\cdot\textbf{r}), \exp(i \textbf{k}\cdot\textbf{r}) \)
- \( \sin(-\textbf{k}\cdot\textbf{r}), \cos(-\textbf{k}\cdot\textbf{r}), \exp(-i \textbf{k}\cdot\textbf{r}) \)
- where \( \textbf{k} \) and \( \textbf{r} \) are vectors
- with de broy’s hypothesis
- \( \lambda = \frac{h}{p} \)
- and the definition \( k = \frac{2\pi}{\lambda} \)
- \( k = \frac{2 \pi p}{h} = \frac{p}{h} \)
- where \( h = \frac{h}{2\pi} \)
- so \( k^2 = \frac{p^2}{h^2} \)
- \( k = \frac{2 \pi p}{h} = \frac{p}{h} \)
- hellholtz equation rewritten
- \( \nabla^2 \psi = -\frac{p^2}{h^2} \psi \)
- \( -h^2\nabla^2\psi = p^2\psi \)
- considering an electron
- \( -\frac{h^2}{2 m_0}\nabla^2\psi = \frac{p^2}{2m_0}\psi \)
- dividing both sides by the mass of an electron
- from classical mechanics
- \( \frac{p^2}{2m_0} = \) kinetic energy of electron
- in general:
- \( E \text{ (total energy) } = \text{ kinetic energy } + \text{ potential energy } (V(\textbf{r})) \)
- Kinetic Energy = Total Energy - Potential Energy
- hellholtz Equation:
- \( -\frac{h^2}{2m_0} \nabla^2 \psi = \frac{p^2}{2m_0} \psi \)
- schrodinger’s equation
- \( -\frac{h^2}{2m_0} \nabla^2 \psi = (E - V(\textbf{r})) \psi \)
- equivalently: \( \left( -\frac{h^2}{2m_0} \nabla^2 + V(\textbf{r}) \right) \psi = E \psi \)
- this is a time independent equation
- \( -\frac{h^2}{2 m_0}\nabla^2\psi = \frac{p^2}{2m_0}\psi \)
schrodinger’s wave equation
- for any mass \( m \):
- \( \left( -\frac{h^2}{2m} \nabla^2 + V(\textbf{r}) \right) \psi = E \psi \)
- this is the time independent shrodinger equation
- there is no first-principles that precede schrodinger’s equation
- it is only postulated
- similar to newton’s gravity theory
probability densities
- born’s postulates
- the probability \( P(\textbf{r}) \) of finding an electron near any specific point \( \textbf{r} \) in space
- probability is proportional to the modulus squared \( \lvert \psi(\textbf{r}) \rvert^2 \)
- of the wave amplitude \( \lvert \psi(\textbf{r}) \rvert \)
- \( \lvert \psi(\textbf{r}) \rvert^2 \): is the probability density
- \( \psi(\textbf{r}) \): probability amplitude (quantum mechanical amplitude)