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In this PDF

http://riedo.gatech.edu/Teaching/Modern_Physics/hw/HW3_2010_MP_SOL.pdf

problem#1, the instructor solves the question of which spherical shell (what radius $r$) has the greatest probability for the 3p hydrogen electron to sit in.

I understand everything except the one step where she throws out a factor of $r^4$.

The wave function for the 3p electron is:

$\dfrac{4}{(81 \sqrt 6)}(6 - r)(r)e^{-r/3}$

(I neglect the $a_0$ factors as, like other constants, they would not affect the calculation of where the points are where $d(probability\_of\_finding\_electron)/dr = 0$.)

Indeed the first steps are to throw out all unnecessary factors: we can dump all constant factors like $a_0$ and $81 \sqrt 6$ as well as the $4\pi$ in the spherical shell surface area expression $4 \pi r^2$

I.e. the probability for each particular shell is

$(4 \pi r^2)(\Delta r) \cdot \Psi^{*} \Psi$

And dumping all the constant factors including $\Delta r$ leaves us with:

$r^2 [(6-r)(r)e^{-r/3}]^2$

=

$r^4 [(6-r)^2 e^{-2r/3}]$

as the expression to be minimized.

Now the instructor then throws out the $r^4$, saying we can neglect solutions at $r=0$.

But doesn't this actually change the expression when you take $d(probability\_of\_finding\_electron)/dr$?

In other words, the zeroes of:

$\frac{d}{dr}(r^4 [(6-r)^2 e^{-2r/3}])$

are different from

$\frac{d}{dr}([(6-r)^2 e^{-2r/3}])$?

Would you please tell me why it's okay to throw out the $r^4$?

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2 Answers 2

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The instructor hasn't thrown out $r^4$. If you do the calculations properly you will get the desired result. What the instructor is telling is that while simplifying and taking commons out for $\frac{\text{dP(r)}}{\text{dr}}=0$ you get,$$(\text r^3)(6-\frac{\text r}{\text a_0})(f(\text r))=0$$which gives, $\text r=0$ and $6\text a_0$ from the first two terms. But these two values correspond to minimum probability positions as obtained from the expression for $\text P(\text r)$ by setting $\text P(\text r)=0$. So, for maximum probability positions the first two terms of the above equation cannot be zero as they are zero for minimum probability positions. Hence, you have to check the solutions from $f(\text r)=0$.

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  • $\begingroup$ I worked through the full calculations and you are correct that it works. I do not understand how you got $\dfrac{6-r}{a_0}$ for $dP/dr$ because substituting $6a_0$ into the expression for $dP/dr$ does not give 0. $\endgroup$
    – a00
    Aug 24, 2015 at 18:42
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    $\begingroup$ Its $6-r/a_0$ when you put $6a_0$ in r you get 6-6=0 $\endgroup$ Aug 24, 2015 at 18:59
  • $\begingroup$ See I suggest you to go with easy mathematics. To find the roots go in a systematic way. Expand the expression and differentiate you will be left with a cubic equation after taking $r^3$ outside. $r^3$ gives one solution at 0 and the cubic equation will give you 3 solutions out of which $6a_0$ corresponds to a minimum probabilty position. $\endgroup$ Aug 24, 2015 at 19:58
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    $\begingroup$ Your explanation makes more sense now. I seem to have had a mental block. Thank you for helping me break through it. $\endgroup$
    – a00
    Aug 26, 2015 at 13:32
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    $\begingroup$ I am going to flag this as the chosen answer because although both yours and Gert's were equally helpful, according to StackExchange yours occurred slightly earlier. $\endgroup$
    – a00
    Aug 26, 2015 at 13:35
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Firstly, you cannot simply 'neglect' $a_0$ (as the *.pdf actually shows).

In some test books the following substitution is used: $\rho=\frac{r}{a_0}$, so the $a_0$ doesn't have to be 'carried around'.

As your expression for $P(\rho)$ is made of three factors, each factor can be evaluated for extrema individually. $\rho=0$ is an obvious minimum from the first factor, $\rho=\infty$ is another from the exponential term.

The middle factor is evaluated by deriving it to $\rho$, setting to $0$ and that gives:

$\frac{2}{3}\rho^2-10\rho+24=0$.

Or $\rho=3$ and $\rho=12$.

Since as $P(\rho)$ is highest for $\rho=12$, we find that the most probable radial position is $r=12a_0$.

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  • $\begingroup$ You are saying that wherever the slope goes to zero for just the MIDDLE term gives you the zeroes of the whole 3 part thing put together. I am a little hazy as to why you are sure of this, but when I work it out using everything I end up with $(4*36) + (-60+-24)\rho + (6+8)\rho^2 + (-2/3)\rho^3$, which gives the same points of slope=0 to be 0, 3, and 12. Thanks for the perspective. $\endgroup$
    – a00
    Aug 24, 2015 at 18:35
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    $\begingroup$ Look at it like this. $(x-1)(x^2-4)(x+3)=0$ has 4 roots: $x=1, x=2, x=-2,x-3$ because you can evaluate the roots of each factor. As long as $x$ has one of these values the left hand always yields $0$. $\endgroup$
    – Gert
    Aug 24, 2015 at 19:39
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    $\begingroup$ @a00 $\rho$=6 does give zero check properly. $\endgroup$ Aug 24, 2015 at 19:52
  • $\begingroup$ Yes, that's true. Although this is not terribly hard stuff, I was getting confused. But it is true that you must take the derivative first before using the rule of "analyzing the pieces for roots separately", because for example of $P(\rho) = r^{10}(6-r)$, the roots of $P()$ are 0 and 6, but the roots of $dP/dr$ are 0 and 60/11. $\endgroup$
    – a00
    Aug 26, 2015 at 13:29
  • $\begingroup$ Gert, thank you for putting it in a way where I can see exactly what you mean, and clearing up the picture in my head. $\endgroup$
    – a00
    Aug 26, 2015 at 13:30

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