3.

Pauli Principle

Contents
Identical particles, permutation symmetry, Pauli principle, Pauli repulsion, Pauli exclusion principle, symmetric and antisymmetric wavefunctions, Fermion and Boson, Slater determinants, permutation symmetry on electronic structure of atoms. Central Concepts Identical particles, permutation symmetry. Difficult Points Construction of proper wavefunctions for a given atomic/molecular system.

Notes 1. Permutation Symmetry of Identical Particles Consider a system consisting a number of electrons which can access the same volume of space. We call these electrons are identical. (However, if the electrons are well separated in space, they are distinguishable because their spatial positions are different.) We may denote the electronic wavefunction as (q1,q2,q3.) with qi representing ALL the parameters of the electron i. i.e. , qi =(ri,pi,msi). Obviously, since all electrons are the same (identical), the wavefunction should reflect such a trivial fact that the wavefunctions should give the same probability distribution of system if two (or more) electrons i and j permute (exchange) their coordinates (qi is changed into qj and vise versa), i.e., (qj,qi,qn.)=c(qi,qj,qn.) where c is a non-zero constant. (1.1)

Now we want to see what type of wavefunction can be selected as the candidate to reflect the aforementioned fact, that is to say, what values the constant c may take. Since permutation is an action that causes the wavefunction change, we can take the permutation of the electrons as an operation just like any other operators. We may rewrite eq.(1.1) as Pij(qi,qj,qn.)(qj,qi,qn.)=c(qi,qj,qn.) (1.2)

Then the task is to find out the eigenvalues of the permutation operator Pij. Suppose that the eigenfunction of Pij. is w(qi,qj,qn.): Pijw(qi,qj,qn.)=cw(qi,qj,qn.) (1.3)

We notice that the repetition of applying Pij on the same eigenfunction returns it back to its original state: PijPijw(qi,qj,qn.)= Pijw(qj,qi,qn.)= w(qi,qj,qn.) (1.4) but on the other hand, we have from the eq.(1.3) that PijPijw(qi,qj,qn.)=c2w( qi,qj,qn.). (1.5) Compare eqs.(1.4,5), we have c2=1 which means c=+1 or -1. Thus we get the result: the wavefunction of a system of identical particles must satisfy this condition: The permutation of the particles causes at most a sign change on the wavefunction. We call the wavefunction symmetric if it upon permutation does not change the sign and anti-symmetric if it does. In other words, only symmetric or antisymmetric wavefunctions are proper candidates for describing a system consisting of identical particles. 2. Pauli Principle According to above section, we can classify the identical systems into two categories: one whose wavefunctions change sign after permutation (anti-symmetric) and the other whose wavefunctions remain the same (symmetric) upon permutation. Wolfgang Pauli found that fermions (particles with odd-half-integer spin quantum numbers 1/2, 3/2, 5/2 etc) belong to the former while bosons (particles with integer spin quantum numbers 0, 1, 2, ) belong to the latter. Because electrons are of spin1/2, it concludes that the wavefunctions of identical electrons must be anti-symmetric

That is called Pauli principle, as we listed as Postulate 6 of quantum mechanics (Lecture 1). We see it is actually a special case of a more general conclusion (in fact, it is a theorem of relativistic quantum field theory). A simple consequence of the Pauli principle is that two electrons cannot stay at the same place because(qi,qi,qn.)=- (qi,qi,qn.)=> (qi,qi,qn.)=0. Namely, the anti-symmetric property of the wavefunction of identical electrons keeps electrons apart as if there were repulsion between them. This virtual repulsive force is called Pauli repulsion. For a composite particle consisting of both fermions and bosons, the symmetry of its wavefunction is determined by the number of fermions and bosons it contains. The general form of the wavefunction can be written as (f1,fnf,b1.bnb) (nf and nb are the number of fermions and bosons) which changes sign with every permutation on a pair of fermions but does not change anything with permutations on bosons. If there are an odd number of fermions, the composite is a fermion, otherwise, it is a boson. Pauli principle offers a good simplification on the selection of wavefunctions for electron systems in atoms and molecules: All wavefunctions that are not antisymmetric are ruled out. The central task, therefore, is to construct the anti-symmetric wavefunctions from the possible state functions. Generally, we have two independent spaces: ordinary geometric space (r) and spin space (S). The total wavefunction can be written as the direct product of the two wavefunctions in those two spaces. Therefore, we have two possibilities: =r s where r is antisymmetric whiles is symmetric orr is symmetric whiles is antisymmetric. Example 1: Ground state of helium atom. It has two electrons. According to above procedure, we first write the symmetric and anti-symmetric wavefunctions in spatial and spin spaces, respectively, and then construct the anti-symmetric total wavefucnions. However, in this case, the problem is simpler: we have only symmetric spatial wavefunciton for helium ground state: 1s(1)1s(2). Therfore, we only ned to find out the anti-symmetric spin states. All possible spin states are (1)(2), (1)(2), (1)(2) and (1)(2). Clearly, the first and fourth are symmetric; the second and third are neither symmetric nor anti-symmetric; none of above are anti-symmetric. Therefore, we need to do some reconstruction job on the second and third states to get the anti-symmetric spin states: i.e., find out proper linear combinations that are anti-

symmetric. The general linear combination is written as c1(1)(2)+c2(1)(2). So the problem is find out proper c1 and c2. We first see what restriction is imposed on c1 and c2 by normalization condition: |c1(1)(2)+c2(1)(2)|2=1 which leads to c1c1*+c2c2*=1 (2.2) (2.1)

[Eq.(2.1) means [c1(1)(2)+c2(1)(2)]*[c1(1)(2)+c2(1)(2)]=1. By using the orthonomal conditions on and : =1, =0, =0, =1, we readily come to eq.(2.2).]

If we apply permute 1 and 2, we get the state c2(1)(2)+c1(1)(2). In order to get anti-symmetric result, we necessarily have c1(1)(2)+c2(1)(2)=-(c2(1)(2)+c1(1)(2)) (2.3)

which means c1=-c2. From eq.(2.2), we have c1=1/2=-c2. Thus we get the antisymmetric spin states as [(1)(2)-(1)(2)]/2 (2.4)

Since the two states in eq.(2.4) differ only by a sign, meaning they are equivalent,. We may take either of them as the state function we need. Usually, we take the plus state. Therefore, we get the correct ground state of helium atom: 1s(1)1s(2) [(1)(2)-(1)(2)]/2 (2.5)

which means that the two electrons have the same spatial wavefunction but have opposite spin orientations. However, we must be careful about the exact meaning of opposite orientationsit is an anti-symmetric combination of two basic spin states. Example 2: First excited state of helium atom. Without considering spin variables, the first excited state is the anti-symmetric combination of 1s and 2s (see Eq.(9.105) on page 268 of the textbook): [1s(1)2s(2)-2s(1)1s(2)]/2. The spin states then have be symmetric for the total wavefunctions to be anti-symmetric. The two possible symmetric states were given before: (1)(2), (1)(2). The other one can be constructed following the same procedure of eqs.(2.1-2.4) and it is [(1)(2)+(1)(2)]/2. Therefore, the correct first excited states of helium atom are

(1)(2) [1s(1)2s(2)-2s(1)1s(2)]/2 (1)(2) [1s(1)2s(2)-2s(1)1s(2)]/2

(2.6a) (2.6b) (2.6c)

[(1)(2)+(1)(2)][1s(1)2s(2)-2s(1)1s(2)]/2 The next excited state of helium is [(1)(2)-(1)(2)][1s(1)2s(2)+2s(1)1s(2)]/2

(2.7)

the combination of antisymmetric spin and symmetric spatial wavefunctions. To a good approximation, the Hamiltonian does not contain spin terms, so the energy is not affected by the inclusion of the spin factor. Only new degeneracy is introduced. However, there do exist interactions involving spins as to be seen later.

3. Pauli Exclusion Principle

Now we turn to three electron systems such as lithium atom. We will see how Paulis anti-symmetry principle imposes more striking restrictions on electronic states. Suppose we have the spatial part of the ground state of lithium atom as 1s(1)1s(2)1s(3) which is symmetric. The spin state then has to be anti-symmetric. How to construct an anti-symmetric wavefunction for a three-spin-1/2 system? The answer is: impossible. How? The proof is as follows: Suppose the basic states (for any variable, not only for spin) of three identical particles are f, g and h. It is easy to find that there are six possible permutations for three identical particles. The possible states are: f(1)g(2)h(3), f(2)g(1)h(3), f(3)g(2)h(1), f(1)g(3)h(2), f(3)g(1)h(2) and f(2)g(3)h(1). The general state of three identical particles can be written as the linear combination of all possible product of the three states as follows: c1f(1)g(2)h(3)+ c2f(2)g(1)h(3)+ c3f(3)g(2)h(1)+ c4f(1)g(3)h(2)+ c5f(3)g(1)h(2)+ c6f(2)g(3)h(1) (3.1) We wan to find the six coefficients c1 through c6 so that eq.(3.1) is anti-symmetric. Suppose we exchange 1 with 2, we get

c1f(2)g(1)h(3)+ c2f(1)g(2)h(3)+ c3f(3)g(1)h(2)+ c4f(2)g(3)h(1)+ c5f(3)g(2)h(1)+ c6f(1)g(3)h(2) (3.2) The anti-symmetry demands that eq.(3.1) differs with eq.(3.2) by only a sign. Since all six basic states are independent of each other That would mean the following relations have to be satisfied: c1=-c2, c3=-c5, c4=-c6 Similarly if we exchange 2 and 3, we get c1f(3)g(2)h(1)+ c2f(2)g(3)h(1)+ c3f(1)g(2)h(3)+ c4f(3)g(1)h(2)+ c5f(1)g(3)h(2)+ c6f(2)g(1)h(3) (3.4) and the following relations c1=-c3, c2=-c4, c5=-c6 Combining eqs.(3.3, 3.5), we have c1=c4=c5=-c2=-c3=-c6 (3.6) (3.5) (3.3)

Therefore, the appropriate anti-symmetric wavefunction is of the form c1[f(1)g(2)h(3)-f(2)g(1)h(3)-f(3)g(2)h(1)+f(1)g(3)h(2)+f(3)g(1)h(2)-f(2)g(3)h(1) (3.7) Using the orthonomality conditions for f, g and h, the normalization condition leads to c1=1/6. Eq.(3.7) can be expressed as a determinant f(1) 1/6 f(2) f(3) g(1) g(2) g(3) h(1) h(2) h(3) (3.8)

therefore, the acceptable wavefunction of a three-identical-particle-system is a threeorder determinant. For three spin-1/2-electron case, we have only two different choices for f, g, h and eq.(3.8) becomes (1) (1) (1)

1/6

(2) (3)

(2) (3)

(2) (3)

(3.9a)

or (1) 1/6 (2) (3) (1) (2) (3) (1) (2) (3) (3.9b)

It is easy to see both eqs.(3.9a, 3.9b) are zero because both have two identical columns. [A determinant is zero if there are two identical columns or rows.] Therefore, we have proved that the anti-symmetric spin state of a three-electron system does not exist. Eq.(3.8) has a famous effect on the electronic states in an atom. We consider both the spatial and spin variables. Denote a spin orbital as 1s(i)(i) for i-th electron. It instantly tells us from eq.(3.8) that it is not possible for two electrons occupy the same spin orbital because the determinant would be zero if, for example, f=1s and g=1s or g=1s and h=1s or f=1s, g=1s and h=1s. This is called Pauli exclusion principle. We see Pauli exclusion principle is a special case of Pauli principle. For lithium atom, we see, it is impossible for three electrons to occupy 1s state. 2s state has to be occupied. This is an example of the fact that there are very important restrictions of the electron spin on atomic structure. According to eq.(3.8), we can construct the following ground state for lithium atom: 1s(1)(1) 1s(1)(1) 2s(1)(1) 1/6 1s(2)(2) 1s(2)(2) 2s(2)(2) 1s(3)(3) 1s(3)(3) 2s(3)(3) (3.10)

4. Slater Determinants

Eq.(3.8) can be extended to more general electronic systems. If ther are n electrons in an atom, the general zero-th order ground state wavefunction can be written as a nthorder determinant, called the Salter determinant: (0)(1,2,,i,..n)= 1(1) 2(1) i(1)n(1) 1(2) 2(2) i(2)n(2) (4.1) 1/n! 1(i) 2(i) i(i)n(i) 1(n) 2(n) i(n)n(n) where1,2i,n are the single particle states (spin orbitals). Eq.(3.11) may also be written as a simplified form as (0)(1,2,,i,..n)=| 1,2,i,,n| where the two vertical lines indicate the formation of determinant and the multiplication of the fact 1/n!. For example, the ground state of helium atom is(0)(1,2)= |1,2|=|1s,1s| which really means (0)(1,2)=1/2 1s(1)(1) 1s(1)(1) 1s(2)(2) 1s(2)(2) (4.2) For excited states, the zero-th order wavefunction may be constructed with simple linear combinations of the Slater determinants. Here simple means that the coefficients in one combination differ at most by a sign. For example, it is straightforward to verify that the excited state configuration 1s2s of helium atom given by eqs.(2.6a,b,c,2.7) can be written as |1s,2s|, |1s,2s|, |1s,2s|+| 1s,2s|/2 and |1s,2s|-|1s,2s|/2,respectively.

5. Ground State Energy of Lithium Atom

In this section, we calculate the ground state energy of lithium atom with perturbation theory and variation method, respectively. The zero-th and perturbation Hamiltonians of lithium atom are H(0)=-(21/2me)-(22/2me)-(23/2me)-Ze2/r1-Ze2/r2-Ze2/r3 (5.1) H=e2/r12+e2/r23+e2/r13 (5.2) 5.1 Why 1s(1)1s(2)1s(3) cannot be the ground state of lithium atom? First we prove that the configuration 1s(1)1s(2)1s(3) violates the variation pinciple by evaluating its energy and comparing it with the experimental result. The zero-th order energy would be for this state (eq.(9.48) in textbook: E(0)=-(1/n2+1/n2+1/n2) (Z2e2/2a0) with n=1,Z=3):

E(0)=-(1/12+1/12+1/12)(Z2e2/2a0)=-27(e2/2a0)=-27(13.6eV)=-367.4 eV (5.3) The first order energy correction is E(1)=|1s(1)|2|1s(2)|2|1s(3)|2(e2/r12)dv+|1s(1)|2|1s(2)|2|1s(3)|2(e2/r23)dv+|1s(1)|2| 1s(2)|2|1s(3)|2(e2/r13)dv (5.4) Because the symmetry of the indices 1, 2 and 3, above equation can be changed into E(1)=|1s(1)|2|1s(2)|2|1s(3)|2(e2/r12)dv+|1s(3)|2|1s(2)|2|1s(1)|2(e2/r21)dv+|1s(1)|2| 1s(3)|2|1s(2)|2(e2/r12)dv (5.5) All three integrals are the same, so we have E(1)=3|1s(1)|2|1s(2)|2|1s(3)|2(e2/r12)dv =3|1s(1)|2|1s(2)|2 (e2/r12)dv1dv2|1s(3)|2 dv3 =3|1s(1)|2|1s(2)|2 (e2/r12)dv1dv2=3(5Ze2/2a0)=153.1 eV (5.6) Therefore the ground state energy is E(0)+E(1)=-214.3 eV where the experimental result (by adding up the first, second and third ionization energies) is (5.39+75.64+122.45) eV=-203.5 eV which is larger than the theoretical result, violating the variation principle. Therefore, the state 1s(1)1s(2)1s(3) cannot describe the correct ground state of lithium atom. 5.2 Perturbation treatment of lithium ground state As we learned before, the correct ground state is given by eq.(3.10). Now we use that zero-order ground state to calculate energy. E(0)=-(1/12+1/12+1/22)(Z2e2/2a0)=-81(e2/2a0)/4=-81(13.6eV)/4=-275.5 eV (5.7) To obtain the first order energy correction, we must calculate <(0)|H(1)|(0)> where (0) and H(1) are given by eq.(3.10) and eq.(5.2), respectively. (0) can be expanded as (0)=[1s(1)1s(2)2s(3)(1)(2)(3) 1s(1)2s(2)1s(3)(1)a(2)(3) - 1s(1)1s(2)2s(3) (1)(2)(3)+ 1s(1)2s(2)2s(3)(1)(2)(3) + 2s(1)1s(2)1s(3)(1)(2)(3) -2s(1)1s(2)1s(3) (1)(2)(3)]6-1/2 (5.7) Which can be re-written as (0)= 6-1/2[1s(1)2s(2)1s(3)-1s(1)1s(2)2s(3)] (1)(2)(3) + 6-1/2[1s(1)1s(2)2s(3)2s(1)1s(2)1s(3)] (1)(2)(3) + 6-1/2[2s(1)1s(2)1s(3)-1s(1)2s(2)1s(3)] (1)(2)(3) =a(1)(2)(3)+ b(1)(2)(3) + c(1)(2)(3)=A+B+C (5.8) a=6-1/2[1s(1)2s(2)1s(3)-1s(1)1s(2)2s(3)] b=6-1/2[1s(1)1s(2)2s(3)-2s(1)1s(2)1s(3)] c=6-1/2[2s(1)1s(2)1s(3)-1s(1)2s(2)1s(3)] (5.9a) (5.9b) (5.9c)

The first order energy correction then is E(1)=d(0)*H(0) (d=dv1dv2dv3) =d(|A|2H+|B|2H+|C|2H+A*BH+B*CH+A*CH+AB*H+BC*H+AC*H) (5.10) Because of the orthonomality conditions of the spin states, all integrals involving cross terms A*B, B*C, A*C,AB*,BC*,AC* are zero (e.g., B*C= [b(1)(2)(3)]* [ c(1)(2)(3)] = b*c*(1) (1)*(2) (2)*(3) (3)=0 since *(2) (2)=0 and also *(3)(3)=0.) Thus, eq.(5.10) becomes E(1) =dv1dv2dv3(|A|2H+|B|2H+|C|2H)=a2Hdv1dv2dv3 +b2Hdv1dv2dv3+b2Hdv1dv2dv3+dv1dv2dv3 (5.11)

Substituting the expressions of a, b, c into above equation and using the orthonomality condition for 1s and 2s orbitals, we get: E(1) =21s2(1)2s2(2)(e2/r12)dv1dv2+1s2(1)1s2(2)(e2/r12)dv1dv2-1s(1)2s(2) 1s(2)2s(1) (e2/r12)dv1dv2 =2J1s2s+J1s1s-K1s2s (5.12) We already had the values of J1s2s, J1s1s and K1s2s before (eqs.(9.52,9.55,9.113)) J1s2s= 5(Ze2/a0)/8, J1s1s=17(Ze2/a0)/81, K1s2s=16(Ze2/a0)/729 (5.13)

Finally, the first order energy correction is found to be E(1) =5965e2/a0)/972=83.5 eV. The energy through the first order is therefore -275.5 eV+83.5 eV=-192.0 eV. It does not violate variation principle although it is still not sufficiently accurate. Higher- order corrections have to be included to further improve the accuracy. 5.2 Variation treatment of lithium ground state According to Table 6.2 (textbook p.149), we use the following trial function as the 1s state: f=(b1/a0)3/2e-b r/a0/1/2
1

(5.14)

and the trial function for the 2s state: g=(b2/a0)3/2(2-b2r/a0)e-b r/a0/4(2)1/2

2

(5.15)

The trial variation function for the ground state of lithium atom then is given by = f(1)(1) f(1)(1) g(1)(1) 1/6 f(2)(2) f(2)(2) g(2)(2) f(3)(3) f(3)(3) g(3)(3) (cf eq.(3.10). The energy correction is W=<|H|>. The best parameters found from W/b1=0 and W/b2=0 are b1=2.686 and b2=1.776 and W=-201.2 eV which is much better than the first order perturbation result. However, there is still some room for further correction by, for example, introducing r12, r23, r13 into the trial function. (5.16)

Summary
The fermionic properties of the electrons demand that the wavefunction must be antisymmetric. One important consequence of Pauli principle is that one spin orbital cannot be occupied by two or more electrons. Anti-symmetric wavefunctions can be constructed by making use of the Slater determinant.

Questions
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Problems
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Applications and Extended Readings/Exercises

References
Textbook pp.285-299. .

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