Radial Probability Distribution Curve versus ψ² versus r curve for 1s orbitals

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It is very important to note here that $R(r)$ is just the radial part of wavefunction. Wavefunction does not describe any observable. The Born interpretation says that the probability density of finding electron between any two points $x_1$ and $x_2$ is given by $$\rho=\psi\psi^*.$$ While the probability is $$P =\int_{x_1}^{x_2}{\psi\psi^* \mathrm{d}x}.$$ (This is only in one dimension. In spherical coordinates you must integrate over the volume).
Why is there a difference between these two quantities? I think it will be easier to understand using an analogy. Consider a rod of unit length in which the charge varies as a function of $x$. Say the function is $$q(x)=x\mathrm{e}^x-1$$ The average charge of the rod is $0$. While the average charge density of this rod is $\mathrm{e}-2$. Where average is given by $$\langle f \rangle=\frac{\int^{b}_{a}{f \mathrm{d}x}}{b-a}.$$ I hope you have understood the difference between function density and the function itself. The radial probability and probability density are something similar. By seeing the graphs you can to a certain extent predict the average of the probability density and probability. In the second graph it is $0$ while in the second graph it is close to the peak which is $a_0$.

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Seshank K
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Seshank K

Updated on August 01, 2022

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  • Seshank K
    Seshank K over 1 year

    My question is basic, but I have already referred to a couple of books.

    This is an excerpt from Linus Pauling's book:

    the most probable distance of the electron from the nucleus, which is the value of $r$ at which $D(r)$ has its maximum value, is seen from Figure 21-1 to be $a=\pu{0.529 \mathring{A}}$, which is just the radius of the normal Bohr orbit for hydrogen.
    [Figure 21-1 is the Radial Probability Distribution Curve (RPDC) for the 1s orbital, see below.]

    And on the next page he states that:

    The function ${\psi^2_{100}}$ has its maximum value at $r=0$, showing that the most probable position for the electron is in the immediate neighborhood of the nucleus; that is, the chance that the electron lie in a small volume element very near the nucleus is larger than the chance that it lie in a volume element of the same size at a greater distance from the nucleus.

    Don't these two statements contradict each other? $\psi^2$ versus $r$ says that the probability density is highest at $r=0$. RPDC says that the probability is highest at $r=\pu{0.529 \mathring{A}}$. Why is there such a stark difference between probability density and probability? When $r$ tends to $0+$ we observe high electron probability density (wrt the $\psi^2$ curve) but minimized electron probability (wrt the RPDF curve)

    I do understand, however, that Radial Probability Distribution Curve represents probability and $\psi^2$ versus $r$ represents probability density. But why is there a difference in these two?

    For reference:

    RPDC curve and psi^2 curve for 1s orbital

    • orthocresol
      orthocresol over 4 years
    • Seshank K
      Seshank K over 4 years
      I do kind of get the language in the answers but the math is kinda advanced for me as a high schooler to understand. Could you please try and word it down for me by reducing the math a bit? That would help a lot. Thanks in advance @orthocresol
    • Seshank K
      Seshank K over 4 years
      And also I agree to all these answers completely with respect to the math. After a while of reading I've almost understood the math entirely but I still have a doubt as to why doesn't chemistry adhere to the mathematics of the equation. Math states that the RPDC curve and psi^2 are same but the same does not hold true when it comes to the arrangement of electrons whereby the electrons are more concentrated closer to r tends to 0+ which is chemically acceptable in the RPDC but mathematically unacceptable. Why?
    • Seshank K
      Seshank K over 4 years
      Correction: "Math states that the RPDC curve and psi^2 are same". What I meant to say was Math says that the graphs are acceptable just the way they are but the chemistry behind the arrangement does not.
    • Nisarg Bhavsar
      Nisarg Bhavsar over 2 years