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Term symbols for electronic configurations are useful not only to the spectroscopist but also to the inorganic chemist interested in understanding electronic and magnetic properties of molecules. We will concentrate on the method of Douglas and McDaniel (p. 26ff); however, you may find other treatments equal or superior to the D & M method. Term symbols are a shorthand method used to describe the energy, angular momentum, and spin multiplicity of an atom in any particular state. The general form is given as aTj where T is a capital letter corresponding to the value of L (the angular momentum quantum number) and may be assigned as S, P, D, F, G, … for |L| = 0, 1, 2, 3, 4, … respectively. The superscript “a” is called the spin multiplicity and can be evaluated as a = 2S +1 where S is the spin quantum number. The subscript “j” is the numerical value of J, a new quantum number defined as: J = l +S, which corresponds to the total orbital and spin angular momentum of the system. The term symbol 3P is read as triplet – Pee state and indicates that there are two unpaired electrons in a state with maximum orbital angular momentum, L=1. The number of microstates (N) of a system corresponds to the total number of distinct arrangements for “e” number of electrons to be placed in “n” number of possible orbital positions. N = # of microstates = n!/(e!(n-e)!) For a set of p orbitals n = 6 since there are 2 positions in each orbital. Therefore, p2 (e = 2 and n = 6) so, N = 6!/(2!(6-2)!) = (6*5*4*3*2*1)/((2*1) * (4*3*2*1)) = 15 We can introduce the idea of a hole formalism which states that for many electronic properties one may consider systems with e or (n-e), the number of unoccupied sites or “holes”, to be equivalent. Thus, P4 (e = 4 and n = 6) N = 6!/(4!(6-4)!) = 15 so P4 (2 holes) and P2 (4 holes) give equivalent values of N. The same is true for all p, d, f, … systems such as d1/d9 or f2/f12. If one should consider an atom with multiple unoccupied orbitals, the total number of microstates will equal the product of the microstates for the individual orbitals. (N = π N*a; a = 1 to i where a = orbital index). For an s1p2 configuration N = 2 (from S1) * 15 (from p2) = 30. We can define component ML in two ways. First, M L = m1 + m2 + m3 + …

L-1. 2. Determine total number of microstates Determine the possible values of ML and MS Determine the Pauli – allowed microstates Set up a chart of microstates Resolve this group of microstates into atomic states The following steps will be illustrated for a d2 configuration. -4. |L-S|. 4. ML will range +4. 5. . It is the absolute magnitude of J that determines the total angular momentum. ML = -4 and MS = +1 since this would require two parallel spins in the same orbital). …. Similar definitions for MS. ML has 2L + 1 values. STEP 1 (Number of Microstates) N = n!/(e!(n-e)! = 10!/(2!*8!) = 45 STEP 2 (Values of ML and MS) For a d orbital. -1 since two electrons may be spin aligned (up or down) or paired. …. ML = L. 0. J.where ml corresponds to the l angular momentum quantum number for each electron in a given orientation. 3. …. The maximum value of ML for 2 electrons is when m1 = +2 and when m2 = +2 or ML = 4 (this can only occur if MS = 0. …. is given as J = L+S. representing the spin of the system may be made with allowable values of MS = 2S+1 The total angular momentum quantum number. Therefore. STEP 3 The Pauli allowed microstates can be drawn as shown on the following pages. The allowed values for MS are 1. Remember that certain combinations of quantum numbers are not allowed (e. Determination of Spectroscopic Terms 1. ml may range from +2 through –2 so there are 5 acceptable ml values.g.. 0. -L where L is the atomic orbital angular momentum. +3. Thus. L+S – 1. Second.

10 microstates for MS = +1 10 microstates for MS = -1 .ML 3 2 1 0 1 0 -1 -1 -2 -3 MS +1 +1 +1 +1 +1 +1 +1 +1 +1 +1 ml = +2 ↑ ↑ ↑ ↑ +1 ↑ ms= +1/2 0 -1 -2 Ms -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 ml = +2 ↓ ↓ ↓ ↓ +1 ↓ ms= -1/2 0 -1 -2 ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↓ ↓ ↓ ↓ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓ By symmetry an equivalent pattern must be observed for ms = -1/2 and MS = -1.

10 (MS = +1) + 10 (MS = -1) + 25 (MS = 0) = 45 microstates as required by Step 1 .ML 4 3 2 1 0 3 2 1 0 -1 2 1 0 -1 -2 1 0 -1 -2 -3 0 -1 -2 -3 -4 MS 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 ml = +2 ↑ ↑ ↑ ↑ ↑ +1 ms= +1/2 0 -1 -2 ml = +2 ↓ +1 ms= -1/2 0 -1 -2 ↓ ↓ ↓ ↑ ↑ ↑ ↑ ↑ ↓ ↓ ↓ ↓ ↓ ↑ ↑ ↑ ↑ ↑ ↓ ↓ ↓ ↓ ↓ ↑ ↑ ↑ ↑ ↑ ↓ ↓ ↓ ↓ ↓ ↑ ↑ ↑ ↑ ↑ ↓ ↓ ↓ ↓ ↓ ↓ These are the 25 microstates for MS = 0 Therefore.

+4 +3 +2 +1 0 -1 -2 -3 -4 1 1 2 2 2 1 1 +1 1 2 3 4 5 4 3 2 1 0 MS 1 1 2 2 2 1 1 -1 ML The sum of the values in this chart must total 45. +3 +2 +1 0 -1 -2 -3 1 1 2 2 2 1 1 +1 1 2 3 4 3 2 1 0 MS 1 1 2 2 2 1 1 -1 ML Elements Removed: 1G (9 microstates) (Notice that the elements removed for 1G came from the MS = 0 column. Table 2. with one from each ML row as required. Chart Microstates On left column put range of ML values On bottom row put range of MS values Then enter the total number of microstates that have equivalent ML and MS values Table 1. Removing 9 microstates from Table 1 yields Table 2.). STEP 5. A 1G representation corresponds to a 9 x 1 matrix (ML x MS) since L can range from +4 through –4 (9 elements) and S can only equal 0 (1 element). the total number of microstates.) . the first term is 1G (We will assign J values later. Resolve Microstates We can immediately see that there is a microstate which must correspond to ML = -4 and MS = 0. This must be a G state since L = 4 and it must be an orbital singlet since MS = 0.STEP 4. Therefore.

Table 4. 3P (44 microstates) This table must correspond to 1S so the d2 configuration gives: 1 G. +2 +1 0 -1 -2 1 1 1 +1 Elements Removed: 1G. so the element is 3F. MS = 0). 3 F is a 7 x 3 matrix = 21 microstates that are removed to give Table 3. 3F.Now go to the upper left corner (italicized and red) element. MS = 1 or a 3P which is a 3 x 3 matrix. 3F (30 microstates) Now got to the single element in row +2 (red) which gives 1D (ML = 2. 3P. ML 0 1 0 MS Elements Removed: 1G. ML +1 0 -1 1 1 1 +1 1 2 1 0 MS 1 1 1 -1 1 2 3 2 1 0 MS 1 1 1 -1 ML Elements Removed: 1G. MS =1 therefore triplet. Table 5. This is a 5 x 1 matrix yielding Table 4. 1D. 1D. The ML and MS value for this element yield the next microstate representation. 1S (45 microstates) . Table 3. This leaves table 5. 1D (35 microstates) Upper left gives ML = 1. 3F. 3F. ML=3 therefore F.

. 1D2. the lowest J corresponds to the lowest energy.e. If the subshell is greater than 1/2 full. and 1D are accounted for. 1S. Ground state will have the largest spin multiplicity i. After checking 1 and 2 above: If the subshell is less than 1/2 full. 3P is lower in energy than 1 P 2. 3F2. We do this by lowering the J value by one until all microstates have been accounted for. S = 0) 5 microstates 3 F ! 3F4 (L = 3.Assigning J Values J = L + S: number of microstates = 2J + 1 G ! 1G4 (L = 4. S = 0) 9 microstates S ! 1S0 (L = 0. This is because we have only calculated the state of maximum multiplicity! Both the 3F and 3P states can be factored.e. The state with the largest L is of lowest energy. 3F4. S = 1) 9 microstates 3 3 P ! P2 (L = 1. 3P1. the highest J corresponds to the lowest energy. 3P0 We must now arrange these in a predicted orbital energy scheme. 3F3. 3P2. Two states with the same spin multiplicity can be distinguished by L values. while 12 3F microstates and 4 3P microstates are missing. For 1 3 3 1 F4 (9 microstates) F3 (7 microstates) 3 F2 (5 microstates) 3 3 21 microstates P2 (5 microstates) P1 (3 microstates) 3 P0 (1 microstate) 9 microstates We now have accounted for all 45 microstates: 1 G4. Thus. Rules for Assigning Energies (Hund’s Rules) 1. i. 1S0. 1D < 1S 3. S = 0) 1 microstate 1 1 D ! D2 (L = 2. S = 1) 5 microstates Notice that the total number of microstates does not equal 45 at this point! All of the microstates associated with 1G.

Spin – orbit coupling (j – j) can have an effect. or empty orbitals represent orbital singlets. the only configuration we are certain of is the ground state. Orbitals with L = odd number have odd parity (ungerade). especially for heavy elements. 5. 2. CAUTION! The energy difference between levels can be less than or equal to the splitting of states.1 S 1 1 S0 D2 G4 1 S D G 1 1 G 3 1 1 P s2p6d2 1 3 D 3 P P2 P1 3 P0 3 3 F 3 F F4 F3 3 F2 3 3 Actual Predicted ground state is 3F2. . Selection rules for transitions ∆l = ±1 ∆S = 0 ∆j = ±1 or 0 3 i. 1/2 filled. The actual order is give at the far right. L and S coupling (Russell – Saunders) is a good description. It usually is not productive to associative a particular electron configuration with a specific term symbol since there can be considerable overlap. For lighter elements. P2 ! 3D3 allowed 1 S0 ! 3P1 not allowed (spin forbidden) 4. Therefore. Miscellaneous Information: 1. Orbitals with L = even number have even parity (gerade). 3.e. Filled.

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