Ground state of Phosphorus Problem

In summary, the problem discussed is from the book "Atomic Physics" by Budker, Kimball, and Demille and involves finding the ground state configuration of Phosphorus with 3 P-state valence electrons. Following Hund's rule, the largest total spin (S) and largest total angular momentum (L) state is desired. The authors use a Slater determinant to find a totally anti-symmetric combination of states for 3 particles, which coincides with the total angular momentum state |L=0, m_L=0\rangle. However, the total angular momentum state L=2 is not addressed, which should also be anti-symmetric and have a lower energy according to Hund's rule. The author later solves their own confusion
  • #1
r_tea
14
0
This problem is 1.1b out of "Atomic Physics" by Budker, Kimball, and Demille. There are solutions in the book, but I am confused:

I'm asked to find the ground state configuration of Phosphorus, which is has 3 P-state valence electrons. Following Hund's rule, we want to find a state with largest total spin (S) and largest total angular momentum (L) (I use little l and s to refer to single particle states). So for 3 electrons, picking the largest S state is easy: we get S=3/2 (i.e. [tex]|m_s=1/2 \rangle|m_s=1/2 \rangle|m_s=1/2 \rangle [/tex]).

Since the spin part is chosen to be symmetric, we must construct an antisymmetric spatial wavefunction. We know all electrons are in the P manifold, so our choices of states for each particle are
[tex] l_i=1, m_{l_i}=1,0,-1 [/tex]

The authors go on to use a Slater determinant to find a totally anti-symmetric combination of these states for 3 particles, which coincides with the total angular momentum state [tex] |L=0, m_L=0\rangle [/tex]. Great! So then the ground state will be
[tex] |S=3/2, m_S= \text{4 possible values}\rangle|L=0, m_L=0\rangle [/tex].

But what the authors don't address is the total angular momentum L=2 state, which should also be anti-symmetric (since symmetry alternates between L=3,2,1,0). And also, since L=2>L=0, it should have a lower energy according to Hund's rules, no? That is my confusion.

Thanks.
 
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  • #2
Actually, I think I solved my own problem. It is true that for two identical spins the total angular momentum states follow the symmetry pattern:
[tex] L_\text{total,max} \rightarrow \text {Symmetric} [/tex]
[tex] L_\text{total,max}-1 \rightarrow \text {Antisymmetric} [/tex]
[tex] L_\text{total,max}-2 \rightarrow \text {Symmetric} [/tex]
[tex] \text{etc.} [/tex]

However, for three particles, I'm pretty sure this statement is not true. For example, in my problem I had the addition of three l=1 particles. I think the states actually look like...
[tex] L_\text{tot}=3 \rightarrow \text {Symmetric} [/tex]
[tex] L_\text{tot}=2 \rightarrow \text {No def symmetry} [/tex]
[tex] L_\text{tot}=1 \rightarrow \text {No def symmetry} [/tex]
[tex] L_\text{tot}=0 \rightarrow \text {Antisymmetric} [/tex]

Hence, only the Ltot=0 case would work for my problem.

Does anyone know any more about this many-particle addition of angular momentum? E.g., maybe the alternating symmetry works for addition of even numbers of identical particles?
 

Related to Ground state of Phosphorus Problem

1. What is the "Ground State of Phosphorus Problem"?

The "Ground State of Phosphorus Problem" refers to the challenge of determining the most stable and lowest energy state of a phosphorus atom or molecule.

2. Why is the Ground State of Phosphorus important?

The ground state of phosphorus is important because it provides valuable information about the electronic structure and chemical reactivity of phosphorus, which is a crucial element in many biological and industrial processes.

3. How is the Ground State of Phosphorus calculated?

The ground state of phosphorus can be calculated using quantum mechanical methods, such as Hartree-Fock theory, density functional theory, or coupled cluster theory. These methods use mathematical equations and computer simulations to determine the most stable arrangement of electrons around the phosphorus atom.

4. What are the factors that affect the Ground State of Phosphorus?

The factors that affect the ground state of phosphorus include the number of electrons and their distribution, the nuclear charge of the phosphorus atom, and the presence of other atoms or molecules in the vicinity that can interact with the phosphorus atom.

5. How does the Ground State of Phosphorus affect its chemical properties?

The ground state of phosphorus plays a crucial role in determining the chemical properties of this element. For example, the number and arrangement of electrons in the ground state can determine the reactivity of phosphorus and its ability to form bonds with other atoms, which ultimately affects its role in various chemical reactions and processes.

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