Path Integral Method in Quantum Mechanics

Guan Wang, University of Chicago

Introduction
In Classical Mechanics, motion is completely described by the least action
principle, is the Lagrangian,
q and are the generalized coordinates and velocity, respectively. In the
following derivation we shall see that starting with a probabilistic construction
of the time dependent state/wavefunction, we can actually recover the action
S of a path as its probability amplitude by insertion of the identity operator at
different times and application of the Trotter Product formula. We then show
that path integrals can be applied to solve for thermodynamic quantities and
the partition function by viewing temperature as imaginary time. At last the
Monte Carlo method of approximating the time-dependent path integral is
illustrated by two examples.

Probability Amplitude of Position Transitions

(Moving from One Point to Another)
We consider only time-independent potentials in this worksheet.
The wavefunction at time t,

where
is the unitary propagator.
Hence
=
So far the theory is exact and the points integrated along the path does not
come into play yet. We will see that those N-1 points were taken to
approximate U(t, t0) as a product of U(ti+1, ti) .

For stationary Hamiltonian, , and this is

not an easy form to evalute for general potentials as momentum and position
operators do not commute.

Hence we use the Trotter product formula, , to get

Therefore =
which the Trotter formula tells us that each segment of the path has action
equivalent to the straight line action from to which is the result of
approximation when step size is small.
Although in some cases (Free particle and Harmonic Oscillator), the integral
can be exact, the infinite dimensional integral is impossible to evaluate
analytically for general potentials.

Analytically Solvable Examples

Free Particle
For free particles, the integral becomes one dimensional as potential term is 0.

For

Harmonic Oscillator
For the path that gives the extremum value of action from

to is

By expanding all paths around this extremal path, the path can be written
as sum of the extremal path and a perturbation , where

The action for this path is then

 then by a change of

variable from x to y, and plugging in the Jacobian of this variable change, we

get

Thus

Path Integral Formulation for Statistical Mechanics

Averages
The canonical ensemble partition fucntion can be written as
where is the density matrix.
Then using the Trotter product formula, it can be expressed as
, which has the same form as the path integral, with .

The related thermodynamic quantities is then just

where is the probability density of the
paths that can be expressed as a trotter product.

Sample Calculations with Monte Carlo Integration

There are two kinds of Path Integral calculations, real time and imaginary
time. Real time path integral calculates the time evolution of a known
wavepacket at some initial time. The imaginary time one calculates ensemble
averages at equilibrium, and the steps to reach is called thermal
equilibriation of the system.
In general, the Monte Carlo Integration is about acquiring samples of a
random variable
integral using the following summation:

Where is the measure of the random variable and is the probability

density distribution of a.

For the thermodynamic path integrals, the probability density function is

already inside the integral and hence the averaged value can be directly
calculated using Monte Carlo Integration via a sample of paths (commonly
sampled by Metropolis-Hastings Algorithm):
 =

So that the hard evaluation of , the PDF of the path is not needed.
But for the time-dependent path integrals, we have no way to cancel the
probability density of any paths inside the integral. So we have to evaluate the
wavefunctions for each step, which is much less efficient than the former
method of direct sampling of entire paths.

The following are two demonstrations of the Monte Carlo Integration method
to calculate evolution of time-dependent wavefunctions.
The first one is a calculation for the free particle wavepacket in one step dt,
sampled with uniform distribution:
>

0.4015427855 (3.1)

The appears in the summation inside the loop as it is the value of ,

where is the number of samples and is the distribution of the random

variable being sampled. In this case as we sample uniformly in the
region between -3.5 and 3.5.
We can then compare this with the analytical result below:

>

where the blue asterisk is the one-step approximation of the red analytical
solution using Monte Carlo Integration. You can try to get more accurate
results by changing 6000 to a larger value, and see if the error increases at
different values of .
The former example showcases the one-step path integral to approximate
evolution of wavepackets in zero potential. For nonzero potentials we need to
break dt into multiple time steps to have accurate results.
The following part initializes samples of given normal distribution in a
Harmonic Oscillator potential with 3 steps:
>
>

>
>
The red curve is the initial wavepacket and the blue asterisks are the -step
approximations on the evolved wavepacket at T=1.
Another example is the minimal basis ground state electron wavefunction for
the Hydrogen atom, which is expected to remain the same no matter the
amount of time passed. This example could potentially serve to test the
accuracy of the minimal basis set in approximating the real ground state:
>
>

With the Quantum Chemistry Package we can show the density plot for the
minimal basis Hartree Fock solution of the H2 molecule:
>
The number of steps and the number of samples at each time step is very
small, so the result would not be accurate. But if you have a large enough
memory, try to modify the code above to include more steps and increase the
sample sizes. Have fun!

References
1. R. P. Feynman, "Space-Time Approach to Non-Relativistic Quantum
Mechanics," Rev. Mod. Phys 20(2), 367-387 (1948).
2. M. Nakahara. Geometry, Topology and Physics (Taylor & Francis Group,
Abingdon, 2003).
3. I. Ruokosenm aki, and T. T. Rantala, "Numerical path integral approach to
quantum dynamics and stationary quantum states," Commun. Comput. Phys.
18, 01 (2015).
4. M. J. E. Westbroek, and P. R.
for evaluating path integrals,"American Journal of Physics 86, 293 (2018).