Quantum Chemistry: approximations using trial functions

3 replies · 3K views · last reply
RubberBandit
Messages
5
Reaction score
0

Homework Statement


For a 3-D, spherically symmetric, isotropic harmonic oscillator, use a trial function e^αr^2 as a variational parameter.

The Hamiltonian as given by the book is attached, as are two files showing screenshots of my attempt at the solution in Mathcad.

I've tried it two ways. In addition to the method I've attached, in which I take the derivative with respect to r of (r^2*(d/dr function)), I also tried (d/dr function)*(r^2)(d/dr function). Neither have worked.

I'm just looking for another set of eyes to look over the math and see where I made an error. I have the solution (it's 3/2 (h/2∏)(k/μ)^1/2. I want to get to the solution myself, I've just been banging my head against this problem for hours now.

The mathcad attatchments are screenshots, so I hope they don't violate the "No scanned photos" policy.

Thanks for any help. :smile:
 
Attachments
  • Equation for the radial kinetic energy operator: H-hat equals minus h-bar squared over 2 mu r squared, times d/dr of (r squared times d/dr), plus k over 2 times r squared.
    Hamiltonian.PNG
    1.1 KB · Views: 458
  • Mathcad worksheet showing a variational calculation: the energy integral with a Gaussian trial function, an intermediate derivative step, the denominator integral, and the final simplified expression for E with a sqrt(2) term over 16 mu alpha.
    Equations 1.PNG
    17.9 KB · Views: 502
  • Mathcad worksheet showing symbolic differentiation of an energy expression with respect to alpha, setting the derivative to zero, solving for alpha as two roots involving h_bar, mu and k, and simplifying the result to 2^(1/4)·h_bar·sqrt(k)·3/(8·sqrt(mu)).
    Equations 2.PNG
    5.8 KB · Views: 461
In the first equation ("What I'm solving"), you forgot the wave function after the potential energy (just inside the last closing bracket):
$$
\frac{k}{2} r^2 e^{-\alpha r^2}
$$
 
Thank you!

Dr. Claude, thank you! That worked! I don't know how I kept missing that, but I did. Thanks for taking a look.