Integration of Spherical Harmonics with a Gaussian (QM)

In summary, the homework statement is to solve an integral that is decomposed into the eigenfunctions of an atom. The first attempt was to use theExpansion Coefficient to find the coefficients, but the Gaussian did not fit into the integral well. The second attempt was to set the initial conditions for the atom so that the eigenfunctions are at the origin, but this required changing the Gaussian into a spherical polar coordinate. If the exponential is pulled out of the integral, it is only non-zero for l = m = 0.
  • #1
Dazzabaijan
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0

Homework Statement


I wish to solve this integral $$b_{lm}(k) = \frac{1}{2(\hbar)^{9/4}(2\pi)^{5/2}\sqrt{\sigma_{px} \sigma_{py} \sigma_{pz}}} \int_{\theta_k = 0}^{\pi}\int_{\varphi_k = 0}^{2\pi} i^l \text{exp}\left[ - \frac{1}{(2\hbar)^2}\left(\frac{(k_z - k_{z0})^2}{\sigma_{pz}^2} + \frac{(k_y - k_{y0})^2}{\sigma_{py}^2} + \frac{(k_x - k_{x0})^2}{\sigma_{px}^2}\right)\right]Y^m_l(\theta_k, \varphi_k) \sin\theta_k d\phi_k d\theta_k$$

which I've obtained from decomposition of a Gaussian into the eigenfunctions of Hydrogen atom.
$$\psi(\textbf{r},0) = \sum_{n=1}^{\infty}\sum_{l=0}^{n-1}\sum_{m=-l}^{l} b_{\textit{nlm}}\varphi_\textit{nlm}(\textbf{r})$$
by performing the scalar product to obtain the expansion coefficient, as such.
$$\begin{equation*}
\begin{split}
\langle\varphi_\textit{nlm}(\textbf{r})|\psi(\textbf{r},0)\rangle &= \langle\varphi_\textit{nlm}(\textbf{r})|\sum_{n=1}^{\infty}\sum_{l=0}^{n-1}\sum_{m=-l}^{l} b_{\textit{nlm}}\varphi_\textit{nlm}(\textbf{r})\rangle\\
&= b_{\textit{nlm}}\sum_{n=1}^{\infty}\sum_{l=0}^{n-1}\sum_{m=-l}^{l}\langle\varphi_\textit{n'l'm'}(\textbf{r})| \varphi_\textit{nlm}(\textbf{r})\rangle\\
&= b_{\textit{nlm}}\sum_{n=1}^{\infty}\sum_{l=0}^{n-1}\sum_{m=-l}^{l}\delta_{n'n}\delta_{l'l}\delta_{m'm}\\
&= b_{nlm}
\end{split}
\end{equation*}$$
Now using two different way of expressing the Gaussian
##\psi(\textbf{r},0)## allowed me to end up with 2 different terms of #b_{nlm}# which I was able to compare.
$$b_{nlm} = \frac{2}{\pi}\int^{\infty}_{k=0}\int^{\infty}_{r=0} R^*_{nl}(\textbf{r}) b_{lm}(k) j_l(kr) r^2 k^2 dr dk <=> N \int^{\pi}_{\theta_k=0}\int^{2\pi}_{\varphi_k=0}\int^{\infty}_{k=0}\int^{\infty} _{r=0} R^*_{nl}(\textbf{r}) i^l j_l(kr) \eta(\textbf{k}-\textbf{k}_0)Y^m_l(\theta_k, \varphi_k) r^2 k^2 \sin\theta_k dr dk d\varphi_k d\theta_k$$

Homework Equations

The Attempt at a Solution


Now I thought if I set the initial conditions ##k_{x0} = k_{y0} = k_{z_0} = 0## and set all the ##\sigma_{pz} = \sigma_{py} = \sigma_{pz} = \sigma## we see that the integral in the beginning $$b_{lm}(k) = \frac{1}{2(\hbar)^{9/4}(2\pi)^{5/2}\sqrt{\sigma_{px} \sigma_{py} \sigma_{pz}}} \int_{\theta_k = 0}^{\pi}\int_{\varphi_k = 0}^{2\pi} i^l \text{exp}\left[ - \frac{|\textbf{k}|^2}{(2\sigma\hbar)^2}\right]Y^m_l(\theta_k, \varphi_k) \sin\theta_k d\phi_k d\theta_k$$
Now that means I'll be able to move the Gaussian out of the integral
$$b_{lm}(k) = \frac{1}{2(\hbar)^{9/4}(2\pi)^{5/2}\sqrt{\sigma_{px} \sigma_{py} \sigma_{pz}}} \text{exp}\left[ - \frac{k^2}{(2\sigma\hbar)^2}\right]\int_{\theta_k = 0}^{\pi}\int_{\varphi_k = 0}^{2\pi} i^l Y^m_l(\theta_k, \varphi_k) \sin\theta_k d\phi_k d\theta_k$$
and then I can perform the rest of the integral and all is fine. But the problem is my project requires for me such that ##k_{y0} \neq 0## and ##k_{x0} = k_{z0} = 0##
And for that to happen I'll have to change my Gaussian into spherical polar coordinate using
$$k_x = k\cos\theta_k\sin\varphi_k$$
$$k_y = k\sin\theta_k\sin\varphi_k$$
$$k_z = k\cos\varphi$$
$$k^2 = k_x^2 + k_y^2 + k_z^2$$
which makes the previous manoeuvre not possible. From what my supervisor said he told me to find a form of Spherical Harmonics that's not defined at the origin? So I'm assuming that there's a form of Spherical Harmonics which I could start at a coordinates same as the Gaussian then I should be able to solve the integral.
 
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  • #2
Check Morse and Feshbach, I think they do something along the line of what you want to do. The other thing, if you pull the exponential out of your integral, the integral is non-zero for [itex] l = m = 0 [/itex] only.
 

FAQ: Integration of Spherical Harmonics with a Gaussian (QM)

1. What is the purpose of integrating spherical harmonics with a Gaussian in quantum mechanics?

The purpose of integrating spherical harmonics with a Gaussian in quantum mechanics is to approximate the wave function of a system in order to solve the Schrödinger equation. This method is often used in computational chemistry to describe the electronic structure of molecules and atoms.

2. How does the integration of spherical harmonics with a Gaussian work?

The integration of spherical harmonics with a Gaussian works by multiplying the spherical harmonics functions, which represent the angular part of the wave function, with a Gaussian function, which represents the radial part of the wave function. The resulting function is then integrated numerically to obtain an approximation of the wave function.

3. What are the advantages of using a Gaussian basis set for integration of spherical harmonics?

Using a Gaussian basis set for integration of spherical harmonics offers several advantages. Firstly, the Gaussian functions are mathematically simple and can be easily manipulated, making the integration process more efficient. Additionally, Gaussian functions can accurately represent the behavior of electrons near the nucleus, where the wave function has a high curvature, which is important for accurate calculations.

4. Are there any limitations to integrating spherical harmonics with a Gaussian?

Yes, there are limitations to integrating spherical harmonics with a Gaussian. One limitation is that the accuracy of the approximation depends on the number of Gaussian functions used, which can make the calculations computationally expensive. Additionally, the Gaussian basis set may not accurately represent the wave function in regions where there are strong interactions between electrons.

5. How is the accuracy of the integration of spherical harmonics with a Gaussian evaluated?

The accuracy of the integration of spherical harmonics with a Gaussian is typically evaluated by comparing the results to experimental data or to more accurate theoretical calculations. Additionally, the convergence of the calculations with increasing number of Gaussian functions can also indicate the accuracy of the approximation.

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