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Many-electron Atoms and Coupling Schemes Questions and Answers

Answer: B

The allowed transition is \({}^{2}\mathrm{P}_{3/2} \rightarrow {}^{2}\mathrm{D}_{5/2}\).

Electric dipole (LS coupling) selection rules: \(\Delta S = 0\), \(\Delta L = 0, \pm 1\) (with a one-electron jump changing \(l\) by \(\pm 1\)), \(\Delta J = 0, \pm 1\), and \(J = 0 \to 0\) forbidden.

For \({}^{2}\mathrm{P}_{3/2} \to {}^{2}\mathrm{D}_{5/2}\): \(\Delta S = 0\), \(\Delta L = +1\), \(\Delta J = +1\). All satisfied.

The others each break a rule. \({}^{1}\mathrm{S}_{0} \to {}^{3}\mathrm{S}_{1}\) changes the spin multiplicity and has \(\Delta L = 0\) between S states. \({}^{2}\mathrm{D}_{5/2} \to {}^{2}\mathrm{P}_{1/2}\) has \(\Delta J = 2\). \({}^{3}\mathrm{P}_{0} \to {}^{5}\mathrm{D}_{0}\) changes the spin and is a \(J = 0 \to 0\) transition.

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2.

The term symbol for the electronic ground state of oxygen atom is

Exam Year(s)

GATE Physics - 2018,

Answer: D

The ground-state term of oxygen is \({}^{3}P_{2}\).

Oxygen is \(1s^{2}2s^{2}2p^{4}\). Hund’s rules for the four 2p electrons:

  1. Maximum spin: place the electrons with \(m_{l} = +1, 0, -1\) spin up and one more spin down, giving \(S = 1\), a triplet.
  2. Maximum \(L\) for that spin: the paired electron goes into \(m_{l} = +1\), so \(M_{L} = 1\) and \(L = 1\), a P term.
  3. The shell is more than half full, so the largest \(J = L + S = 2\) lies lowest.

\({}^{3}P_{0}\) would be the ground state for a less-than-half-filled p shell such as carbon (\(2p^{2}\)). \({}^{1}D_{2}\) and \({}^{1}S_{0}\) are excited terms of the same configuration, with lower spin.

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3.

An excited state of Ca atom is [Mg]3p54s23d1. The spectroscopic terms corresponding to the total orbital angular momentum are

Exam Year(s)

GATE Physics - 2022,

Answer: B

The terms are P, D, and F.

Closed shells and the filled 4s2 subshell contribute no angular momentum. What remains is a 3p5 configuration, which behaves like a single p hole with \(l_{1} = 1\), and one 3d electron with \(l_{2} = 2\). Their orbital angular momenta couple to

\[ L = |l_{1} - l_{2}|, \ldots, l_{1} + l_{2} = 1, 2, 3 \]

giving P, D and F terms. S would need \(L = 0\), impossible when \(l_{1} \ne l_{2}\), so the options containing S are wrong, and 'P and D' omits \(L = 3\).

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4.

The atomic number of an atom is 6. What is the spectroscopic notation of its ground state, according to Hund’s rules?

Exam Year(s)

GATE Physics - 2023,

Answer: A

The ground state is \({}^{3}P_{0}\).

Atomic number 6 is carbon, \(1s^{2}2s^{2}2p^{2}\). Only the two 2p electrons matter. Hund's rules then fix the term:

  1. Maximum spin: the electrons take parallel spins, so \(S = 1\) and the multiplicity is \(2S + 1 = 3\).
  2. Maximum orbital angular momentum allowed with parallel spins: \(m_{l} = +1\) and \(0\), so \(L = 1\), a P term.
  3. The subshell is less than half filled, so the lowest level has the smallest \(J = |L - S| = 0\).

\({}^{3}P_{1}\) would apply only if \(J\) took the middle value, and \({}^{3}P_{2}\) would be the ground state for a more than half-filled shell such as oxygen. \({}^{3}D_{3}\) needs \(L = 2\), impossible for two parallel p electrons, and \({}^{3}S_{1}\) needs \(L = 0\).

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Answer: C

\(K_{\alpha}\) has high intensity and higher wavelength compared to \(K_{\beta}\).

\(K_{\alpha}\) lines come from electrons falling from the L shell into a K-shell vacancy, and \(K_{\beta}\) from the M shell. The L to K gap is smaller than the M to K gap, so the \(K_{\alpha}\) photon has less energy and therefore a longer wavelength, since \(\lambda = hc/E\).

The L to K transition is also much more probable than M to K, because the L shell is closer and more strongly coupled, so \(K_{\alpha}\) is the more intense line, typically several times stronger than \(K_{\beta}\). The other options reverse one or both of these comparisons.

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6.

The total number of electrons in d orbital in Fe2+ ion (atomic number of Fe is 26) is not equal to that of the total number of :

Exam Year(s)

MH SET - 2018, SET Exam - 2018,

Answer: C

The number that differs is the number of p electrons in the Cl− ion.

Fe is [Ar] 3d6 4s2; Fe2+ loses the two 4s electrons and keeps 3d6, so it has 6 d electrons.

  • Ne, 1s2 2s2 2p6: 6 p electrons.
  • Fe atom, 3d6: 6 d electrons.
  • Mg, 1s2 2s2 2p6 3s2: 6 s electrons.
  • Cl−, 18 electrons, 1s2 2s2 2p6 3s2 3p6: 12 p electrons.

Only Cl− does not match the 6 of Fe2+.

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Answer: B

The values are \( j = \frac{5}{2} \) and \( \frac{3}{2} \), with \( m_{j} = \pm\frac{5}{2}, \pm\frac{3}{2}, \pm\frac{1}{2} \).

A d electron has \( l = 2 \) and \( s = \frac{1}{2} \), so \( j = l \pm s = \frac{5}{2} \) or \( \frac{3}{2} \). For each \( j \), \( m_{j} \) runs from \( -j \) to \( +j \) in steps of 1, so together the values are \( \pm\frac{5}{2}, \pm\frac{3}{2}, \pm\frac{1}{2} \).

Integer \( j \) values such as 2, 1 or 3 are impossible for a single electron, whose half-integer spin makes \( j \) half-integral. \( m_{j} = 5, 3, 1, \ldots \) doubles the correct values, and \( m_{j} \) must lie between \( -j \) and \( +j \).

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8.

The S, L and J values that correspond to each of the following states \(^{1}S_{0}\), \(^{3}P_{2}\) are :

Exam Year(s)

MH SET - 2019, SET Exam - 2019,

Answer: A

The values are S = 0, L = 0, J = 0 and S = 1, L = 1, J = 2.

A term symbol \(^{2S+1}L_{J}\) gives the multiplicity 2S + 1 as a superscript, L as a letter (S = 0, P = 1, D = 2) and J as a subscript.

For \(^{1}S_{0}\): 2S + 1 = 1 so S = 0, the letter S means L = 0, and J = 0. For \(^{3}P_{2}\): 2S + 1 = 3 so S = 1, P means L = 1, and J = 2. Option B reads the superscript as S itself, giving S = 1 and S = 2, and options C and D mix up L.

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9.

Which of the both sequences represent an increasing order of orbital energy ?

Exam Year(s)

MH SET - 2019, SET Exam - 2019,

Answer: D

The sequences in increasing order are 3p, 4s, 3d, 4p & 2p, 3s, 3p, 4s.

By the (n + l) rule, orbitals fill in order of increasing n + l, and for equal n + l the one with lower n comes first: 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d and so on. Both sequences in option D follow this order.

Option A's second sequence puts 3d before 4s. Option B puts 3d before 4s in its first sequence. Option C's second sequence puts 5s before 3d and 4f before 4p, both reversed.

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10.

Te2+ ion has two d electrons in its outermost shell. With the aid of Hund's rule the ground term for the d2 system will be :

Exam Year(s)

MH SET - 2020, SET Exam - 2020,

Answer: B

The ground term is \(^{3}F\), with \(M_{L} = 3\) and \(M_{S} = 1\).

Apply Hund's rules to two d electrons (\(m_{l} = 2, 1, 0, -1, -2\)):

  1. Maximise S: put the two electrons in different orbitals with parallel spins, so \(M_{S} = \frac{1}{2} + \frac{1}{2} = 1\), S = 1, multiplicity 3.
  2. Then maximise L: place them in \(m_{l} = 2\) and \(m_{l} = 1\), so \(M_{L} = 3\), L = 3, an F term.

The ground term is \(^{3}F\) (with J = 2 for a shell less than half full, \(^{3}F_{2}\)), as for \(Ti^{2+}\) or \(V^{3+}\). A doublet such as \(^{2}D\) belongs to a single d electron, and a quintet (\(M_{S} = 2\)) would need four unpaired electrons.

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