How to simplify the diatomic molecule Hamiltonian using an expansion?

In summary: What they are doing is substituting in the expression for ##V(r)## for the potential energy part of ##H## and solving for ##V(r)##.
  • #1
MathematicalPhysicist
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Homework Statement


I have the diatomic molecule hamiltonian given by:
$$-\hbar^2/(2\mu)d^2/dr^2+\hbar^2\ell(\ell+1)/(2\mu r^2)+(1/4)K(r-d_0)^2$$

Now it's written in my solutions that if we put:
$$K\equiv 2\mu \omega_0^2, \hbar^2\ell(\ell+1)/(2\mu d_0^4)\equiv \gamma_{\ell} K, r-d_0\equiv \rho$$

Expand to second order in ##\rho## and drop terms in ##\gamma_{\ell}^2## since ##\gamma_{\ell}\ll 1##, to get:
$$-\hbar^2/(2\mu)d^2/dr^2+(1/2)\mu \omega_0^2[(1+12\gamma_{\ell})(\rho - 4\gamma_{\ell}d_0)^2+4\gamma_{\ell}d_0^2]$$

How to get the last expression explicitly?

Homework Equations

The Attempt at a Solution


I thought of expanding ##1/(\rho+d_0)^2 \approx 1/(d_0^2)[1-2\rho/d_0+3\rho^2/d_0^2]##
But I don't see how did they get this expression for the Hamiltonian?
edit: I have edited and corrected the typo.
 
Last edited:
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  • #2
MathematicalPhysicist said:
Expand to second order in ##\rho## and drop terms in ##\gamma_{\ell}$ since $\gamma_{\ell}\ll 1##, to get:
Due to the typo, we can't tell what order of approximation in ##\gamma_{\ell}## is to be made.

I thought of expanding ##1/(\rho+d_0)^2 \approx 1/(d_0^2)[1-2\rho/d_0+3\rho^2/d_0^2]##
Sounds good.
But I don't see how did they get this expression for the Hamiltonian?
The only thing that is required is for their way of writing H to agree with your way of writing H to the assumed orders of approximation in ##\rho## and ##\gamma_{\ell}##. They are probably choosing to write H in a particular way in order to simplify further analysis.
 
  • #3
TSny said:
Due to the typo, we can't tell what order of approximation in ##\gamma_{\ell}## is to be made.

Sounds good.
The only thing that is required is for their way of writing H to agree with your way of writing H to the assumed orders of approximation in ##\rho## and ##\gamma_{\ell}##. They are probably choosing to write H in a particular way in order to simplify further analysis.
I corrected the typo, we should drop terms of order ##\gamma_{\ell}^2## since ##\gamma_{\ell}\ll 1##.
 
  • #4
MathematicalPhysicist said:
I corrected the typo, we should drop terms of order ##\gamma_{\ell}^2## since ##\gamma_{\ell}\ll 1##.
OK.

You are on the right track to use your expansion ##1/(\rho+d_0)^2 \approx 1/(d_0^2)[1-2\rho/d_0+3\rho^2/d_0^2]## in the expression

##V(r) \doteq \hbar^2\ell(\ell+1)/(2\mu r^2)+(1/4)K(r-d_0)^2##

Then you can manipulate your expression for ##V(r)## into their corresponding expression. (Keep in mind that any terms of order ##\gamma_{\ell}^2## may be neglected.) The motivation for doing all this is that, in their expression, the potential energy part of ##H## is just that of a 1D simple harmonic oscillator.
 

What is a diatomic molecule Hamiltonian?

A diatomic molecule Hamiltonian is a mathematical representation of the total energy of a diatomic molecule. It takes into account the kinetic and potential energies of the two atoms that make up the molecule, as well as any interactions between them.

Why is the diatomic molecule Hamiltonian important?

The diatomic molecule Hamiltonian is important because it allows scientists to accurately predict the behavior and properties of diatomic molecules. It is a fundamental concept in quantum mechanics and is used in many areas of chemistry and physics.

What are the components of the diatomic molecule Hamiltonian?

The diatomic molecule Hamiltonian can be broken down into three main components: the kinetic energy operator, the potential energy operator, and the interaction term. The kinetic energy operator describes the movement of the atoms, the potential energy operator describes the forces between the atoms, and the interaction term accounts for any interactions between the atoms.

How is the diatomic molecule Hamiltonian solved?

The diatomic molecule Hamiltonian is solved by using mathematical techniques such as perturbation theory, variational methods, or numerical methods. These methods allow scientists to calculate the energy levels and wavefunctions of the diatomic molecule, which can then be used to predict its behavior and properties.

What factors can affect the accuracy of the diatomic molecule Hamiltonian?

The accuracy of the diatomic molecule Hamiltonian can be affected by several factors, including the level of approximation used in the calculations, the complexity of the molecule, and the accuracy of the experimental data used to validate the calculations. Additionally, the accuracy may also be affected by the choice of basis set and the computational method used.

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