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The electronic spectra of complexes
The electronic spectra of atoms 13.1 Spectroscopic terms 13.2 Terms of a d2 configuration The electronic spectra of complexes 13.3 Ligand-field transitions 13.4 Charge-transfer bands 13.5 Selection rules and intensities 13.6 Luminescence 13.7 Spectra of f-block complexes 13.8 Circular dichroism 13.9 Electron paramagnetic resonance Bonding and spectra of M-M bonded compounds 13.10 The ML5 fragment 13.11 Binuclear complexes
Spectroscopic terms The Russell Saunders Coupling Scheme
Quantum Numbers Electrons in an atom reside in shells characterised by a particular value of n, the Principal Quantum Number. Within each shell an electron can occupy an orbital which is further characterised by an Orbital Quantum Number, l, where l can take all values in the range: l = 0, 1, 2, 3, ... , (n-1), traditionally termed s, p, d, f, etc. orbitals. Each orbital has a characteristic shape reflecting the motion of the electron in that particular orbital, this motion being characterised by an angular momentum that reflects the angular velocity of the electron moving in its orbital. A quantum mechanics approach to determining the energy of electrons in an element or ion is based on the results obtained by solving the Schrödinger Wave Equation for the Hatom. The various solutions for the different energy states are characterised by the three quantum numbers, n, l and ml. ml is a subset of l, where the allowable values are: ml = l, l-1, l-2, ..... 1, 0, -1, ....... , -(l2), -(l-1), -l. There are thus (2l +1) values of ml for each l value, i.e. one s orbital (l = 0), three p orbitals (l = 1), five d orbitals (l = 2), etc. There is a fourth quantum number, ms, that identifies the orientation of the spin of one electron relative to those of other electrons in the system. A single electron in free space has a fundamental property associated with it called spin, arising from the spinning of an asymmetrical charge distribution about its own axis. Like an electron moving in its
orbital around a nucleus, the electron spinning about its axis has associated with its motion a well defined angular momentum. The value of ms is either + ½ or - ½. In summary then, each electron in an orbital is characterised by four quantum numbers:
Quantum Numbers n l Principal Quantum Number - largely governs size of orbital and its energy Azimuthal/Orbital Quantum Number - largely determines shape of orbital Spin Quantum Number - either + ½ or - ½ for single electron
ml Magnetic Quantum Number ms
Russell Saunders coupling The ways in which the angular momenta associated with the orbital and spin motions in many-electron-atoms can be combined together are many and varied. In spite of this seeming complexity, the results are frequently readily determined for simple atom systems and are used to characterise the electronic states of atoms. The interactions that can occur are of three types.
• • •
spin-spin coupling orbit-orbit coupling spin-orbit coupling
There are two principal coupling schemes used:
Russell-Saunders (or L - S) coupling and j - j coupling.
In the Russell Saunders scheme it is assumed that spin-spin coupling > orbit-orbit coupling > spin-orbit coupling. This is found to give a good approximation for first row transition series where J coupling is ignored, however for elements with atomic number greater than thirty, spinorbit coupling becomes more significant and the j-j coupling scheme is used.
2G. 2H. 1F. 2 x 3F.the resultant spin quantum number for a system of electrons.d6 H. 2P d3. hence (2S+1) = 2 L=2 and the Ground Term is written as 2D The Russell Saunders term symbols for the other free ion configurations are given in the Table below. 3G. 2F. Multiplicity occurs when several levels are close together and is given by the formula (2S+1).d7 d4. The overall spin S arises from adding the individual ms together and is as a result of coupling of spin quantum numbers for the separate electrons.1S P. 2 x 2D. for a d1 configuration: S= + ½. 2 x 1D. 3D. 2 x 1S . These states or term letters are represented as follows: Total Orbital Momentum L 0 S 1 P 2 D 3 F 4 G 5 H Spin-Orbit coupling Coupling occurs between the resultant spin and orbital momenta of an electron which gives rise to J the total angular momentum quantum number. The Russell Saunders term symbol that results from these considerations is given by: L As an example.1D. 2 x 3P. (2S+1) Terms for 3dn free ion configurations Configuration d1.Spin-Spin coupling S .d 2 8 2 3 4 5 Ground Term D F F D 3 4 3 Excited Terms P. 1I. 1G.d9 d . Orbit-Orbit coupling L .the total orbital angular momentum quantum number defines the energy state for a system of electrons. 2 x 1G.
2 x 2F.d5 6 4 S 2 G. L is -2*1= -2 Total value of L is therefore +4 +2 +0 -1 -2 or L=3. simply sum the unpaired electrons using a value of ½ for each. . so L for that box is 1*2= 2 in the 0 box is 1 electron. 2P. The two rules are: 1) The Ground Term will have the maximum multiplicity 2) If there is more than 1 Term with maximum multipicity. use the labels for each column to determine the value of L for that box. L is 0 in the -1 box is 1 electron. so L for that box is 2*2= 4 in the +1 box are 2 electrons. A simple graphical method for determining just the ground term alone for the free-ions uses a "fill in the boxes" arrangement. 4F. 4P. 2H. 4D. then add all the individual box values together. To calculate L. then the Ground Term will have the largest value of L. then: in the +2 box are 2 electrons. dn d1 d2 d d d d d 3 4 5 6 2 1 0 -1 -2 L 2 3 3 2 0 S 1/2 1 3/2 2 5/2 2 3/2 1 Ground Term 2 3 4 5 6 5 4 3 2 D F F D S D F F ¯ ¯ ¯ ¯ ¯ ¯ 2 3 3 d7 8 9 d ¯ ¯ ¯ ¯ 2 1/2 D To calculate S. L is -1*1= -1 in the -2 box is 1 electron. 2 x 2G. 2S Note that dn gives the same terms as d10-n Hund's Rules The Ground Terms are deduced by using Hund's Rules. 3 x D. 2I. For a d7 configuration.
The effect of a crystal field on different orbitals in an octahedral field environment will cause the d orbitals to split to give t2g and eg subsets and the D ground term states into T2g and Eg. d4. Russell-Saunders Terms S P D F A1g T1g Eg . The overall result shown in the Table above is that: 4 configurations (d1. p. t2g and a2g. A d1 configuration can be treated as similar to a d9 configuration. Note that it is important to recognise that the F ground term here refers to states arising from d orbitals and not f orbitals and depending on whether it is in an octahedral or tetrahedral environment the lowest term can be either A2g or T1g. The other thing to note is the idea of the "hole" approach. By analogy. d9) give rise to D ground terms. etc. 4 configurations (d2. d3. (where upper case is used to denote states and lower case orbitals). The ground term energies for free ions are also affected by the influence of a crystal field and an analogy is made between orbitals and ground terms that are related due to the angular parts of their electron distribution. f orbitals are split to give subsets known as t1g. The Crystal Field Splitting of RussellSaunders terms in high spin octahedral crystal fields. The magnitude of the d orbital splitting is generally represented as a fraction of Doct or 10Dq. the F ground term when split by a crystal field will give states known as T1g. The Crystal Field Splitting of Russell-Saunders terms The effect of a crystal field on the different orbitals (s. T1g . In the first case there is 1 electron and in the latter there is an absence of an electron ie a hole. T2g Crystal Field Components . depending on whether they are in an octahedral or tetrahedral environment. This is why L for a d1 configuration is the same as for a d6.Note that for 5 electrons with 1 electron in each box then the total value of L is 0. and A2g. T2g. d7. d. d8) give rise to F ground terms and the d5 configuration gives an S ground term. d6.) will result in splitting into subsets of different energies. T2g A2g .
. Eg . for simplicity. symmetric to principal Cn Non-degenerate orbital. except that the symmetry label g (gerade) is absent. F or S which in high spin octahedral fields gives rise to A. have been applied to these states but for this purpose they are written in CAPITAL LETTERS. T2g Note that. spin multiplicities are not included in the table since they remain the same for each term. T2g Eg . unsymmetric to principal Cn Doubly degenerate orbital Triply degenerate orbital Symmetric with respect to center of inversion Unsymmetric with respect to center of inversion Symmetric with respect to C2 perp. This means that the states are either nondegenerate. Mulliken Symbols Mulliken Symbol for atomic and molecular orbitals a b e t (subscript) g (subscript) u (subscript) 1 (subscript) 2 (superscript) ' (superscript) " Explanation Non-degenerate orbital. T1g . E or T states. The table above shows that the Mulliken symmetry labels. The ground term for first-row transition metal ions is either D. T2g A1g . T1g . to principal Cn Unsymmetric with respect to C2 perp.G H I A1g . 2 x T1g . doubly degenerate or triply degenerate. developed for atomic and molecular orbitals. A2g . Eg . to principal Cn Symmetric with respect to sh Unsymmetric with respect to sh For splitting in a tetrahedral crystal field the components are similar.
2 Terms of a d2 configuration The electronic spectra of complexes The spectra of the aqua ions for some first row transition metal ions are shown below. d3.We are now ready to consider how spectra can be interpreted in terms of energy transitions between these various levels. these free ion configurations give rise to F ground states which in octahedral and tetrahedral fields are split into terms designated by the symbols A2(g). Using the Russell-Saunders (LS) coupling scheme. in the interpretation of spectra. . created to display the energy levels. To derive the energies of these terms and the transition energies between them is beyond the needs of introductory level courses and is not covered in general textbooks[10.3 Ligand-field transitions The observation of 2 or 3 peaks in the electronic spectra of d2. What is necessary is an understanding of how to use the diagrams. Use of Orgel diagrams A simplified Orgel diagram (not to scale) showing the terms arising from the splitting of an F state is given below. T2(g) and T1(g). The spin multiplicity and the g subscripts are dropped to make the diagram more general for different configurations. Two types of diagram are available: Orgel and Tanabe-Sugano diagrams. d7 and d8 high spin octahedral complexes requires further treatment involving electron-electron interactions. *13. A listing of some of them is given here as an Appendix. 13.11].
d8 octahedral complexes and d7 tetrahedral complexes. 3 peaks can be predicted which would correspond to the following transitions: 1.I.I.000 cm-1 (for strong field complexes). Peak positions for some octahedral Cr(III) complexes (in cm-1). 3. 2. This corresponds to the energy found from the first transition above and as shown in Table 1 is generally between 15. d7 octahedral complexes. represents the configuration interaction which is generally either taken to be small enough to be ignored or taken as a constant for each complex. Table 1.000 cm-1 (for weak field complexes) and 27. The right-hand side is applicable to d2 . The lines for the two T1 terms are curved to obey the non-crossing rule and as a result introduce a configuration interaction in the transition energy equations.I. Here C.The lines showing the A2 and T2 terms are linear and depend solely on D. In the laboratory component of the course we measure the absorption spectra of some typical chromium(III) complexes and calculate the spectrochemical splitting factor. transition energy = 6/5 *D + 15B' + C. Complex n1 n2 n3 n2/n1 n1/n2 D/B Ref . 4 4 T2g ¬4A2g T1g(F) ¬4A2g 4 T1g(P) ¬4A2g transition energy = D transition energy = 9/5 *D . The left-hand side is applicable to d3 . D.C. Looking at the d3 octahedral case first.
2.576 D/B 5 Ref 13 .45 1.41 1.32 1.I.4 21.4 13 13 This work 4 This work 4 This work 4 4 4 For octahedral Ni(II) complexes the transitions would be: 1.46 1. Peak positions for some octahedral Ni(II) complexes (in cm-1).708 0. 3.32 1.4 24.686 0.758 0.690 0.710 0.748 0.34 1.21 0. Complex NiBr2 n1 6800 n2 11800 n3 20600 n2/n1 1.6 33. transition energy = 6/5 *D + 15B' + C.5 32.37 1.C.756 0. For M(II) ions the size of D is much less than for M(III) ions (around 2/3) and typical values for Ni(II) are 6500 to 13000 cm-1 as shown in Table 2.33 1.Cr3+ in emerald K2NaCrF6 [Cr(H2O)6]3+ Chrome alum [Cr(C2O4)3]3[Cr(NCS)6]3[Cr(acac)3] [Cr(NH3)6]3+ [Cr(en)3]3+ [Cr(CN)6]3- 16260 16050 17000 17400 17544 17800 17860 21550 21600 26700 23700 23260 24000 24500 23866 23800 23800 28500 28500 32200 37740 35460 37500 37800 ? ? ? ? ? ? 1.829 20.752 0.2 28.1 31. where C.I.0 52.74 n1/n2 0.36 1. 3 T2g ¬3A2g 3 T1g(F) ¬3A2g 3 T1g(P) ¬3A2g transition energy = D transition energy = 9/5 *D .5 29. again is the configuration interaction and as before the first transition corresponds exactly to D.0 31.I. Table 2.735 0.
I.2 10. The transition energies of these terms are clearly different and it is often necessary to calculate (or estimate) values of B.64 1.I.8 Ref 13 Interpretation of the spectrum highlights the difficulty of using the right-hand side of the Orgel diagram above for many d2 cases where none of the transitions correspond exactly to D and often only 2 of the 3 transitions are clearly observed. for both arrangements and then evaluate the answers to see which fits better.D and C. But.64 1.608 0. depending on the size of the ligand field (D) the second transition may be due to: 3 A2g¬ 3T1g transition energy = 9/5 *D + C. 3 for a weak field or T1g(P) ¬ 3T1g transition energy = 3/5 *D + 15B' + 2 * C.659 11.63 1. Table 3.6 11.17400 = 17100 cm-1. Peak positions for an octahedral V(III) complex (in cm-1).62 1.690 D/B 30. Given that we expect D to be greater than 15000 cm-1 then we must interpret the second .614 0.I. The first transition can be unambiguously assigned as: 3 T2g¬ 3T1g transition energy = 4/5 *D + C.52 0.[Ni(H2O)6]2+ [Ni(gly)3][Ni(NH3)6]2+ [Ni(en)3]2+ [Ni(bipy)3]2+ 8500 10100 10750 11200 12650 13800 16600 17500 18350 19200 25300 27600 28200 29000 ? 1. few examples have been published.17400 = 7800 cm-1 or 34500 . for a strong field. One such is V3+ doped in Al2O3 where the vanadium ion is generally regarded as octahedral. Table 3.I. In this case D is equal to either: 25200 . The difference between the 3A2g and the 3T2g (F) lines should give D.616 0.6 10. Complex V3+ in Al2O3 n1 17400 n2 25200 n3 34500 n2/n1 1.6 17 13 13 13 3 3 For d2 octahedral complexes.45 n1/n2 0.610 0.
6 from which B' can be calculated as 661 cm-1. N. a series of equations have been determined that can be used to calculate both B and D. The third peak can then be predicted to occur at 69. ie of the first to second transition and so both values are recorded in the Tables.transition as to the 3T2g(P) and the third to 3A2g. The second is that spin-forbidden terms are shown and third that low-spin complexes can be interpreted as well. The procedure used to interpret the spectra of complexes using Tanabe-Sugano diagrams is to find the ratio of the energies of the second to first absorption peak and from this locate the position along the X-axis from which D/B can be determined. since for the d4 . Using Tanabe-Sugano diagrams The first obvious difference to the Orgel diagrams shown in general textbooks is that Tanabe-Sugano diagrams are calculated such that the ground term lies on the X-axis. using the observed peaks found for [Cr(NH3)6]3+ in Table 1 above then. Another approach has been to use the inverse of this ratio. as 3720 cm-1 and B' as 567 cm-1. D/B' is found at 32. Tanabe-Sugano diagrams become a better method for interpreting spectra of d2 octahedral complexes.I.B. When only two transitions are observed. Having found this value.6. . This approach still requires some evaluation of the numbers to ensure a valid fit. Solving the equations like this for the three unknowns can ONLY be done if the three transitions are observed. then tracing a vertical line up the diagram will give the values (in E/B units) of all spin-allowed and spin-forbidden transitions. Further evaluation of the expressions then gives C. For this reason. The E/B' for the first transition is given as 32. As an example.64 * 661 = 46030 cm-1 or 217 nm (well in the UV region and probably hidden by charge transfer or solvent bands).d7 diagrams a vertical line is drawn separating the high and low spin terms. which is given in units of D/B. from the JAVA applet described below.
For the V(III) example treated previously using an Orgel diagram. the value of D/B' determined from the appropriate JAVA applet is around 30.8. .
The position of absorption peaks in the spectra allow the direct measurement of ∆.5) The Laporte Rule. the techniques are valuable. Charge-transfer bands Selection rules and intensities Electronic Absorption Spectroscopy The d-d transitions in complex ions correspond to absorptions which are often. the colours of the complexes are usually relatively pale. This complex is sometimes very pale pink due to the presence of very small amounts of impurities.Spin Forbidden Transitions which would require an electron to change its spin are strongly forbidden. owe their colour to charge-transfer transitions which involve the excitation of an electron from a molecular orbital largely centered on the metal to one largely centered on the ligands or vice versa. though not always. significantly larger than the 17100 cm-1 calculated above and shows the sort of variation expected from these methods. In a molecule or ion possessing a centre of symmetry. Consider the case of the high spin d5 complex [Mn(H2O)6]2+. bear in mind that allowed and Laporte forbidden transitions can occur outside the visible region of the spectrum if the crystal field splitting is very large. This is particularly straightforward for ions with a d1 or d10 configurations. Selection Rules for d-d Transitions and Colour Intensity (Section 13. This can happen with strong field ligands such as CN¯ or CO. Spin Allowed . The average value of B' calculated from the three Y-intercepts is 598 cm-1 hence D equals 18420 cm-1. The reason transitions are observed at all is because the symmetry centre is transiently destroyed by vibrations of the molecules or ions. for example d to d.Following the vertical line upwards leads to the assignment of the first transition to 3 T2g¬3T1g and the second and third to 3T1g (P) ¬3T1g (blue line) and 3A2g¬3T1g (green line) respectively. usually very intensely coloured. As examples. In cases where the rule applies. The geometries affected by this rule include octahedral and square-planar depending on the ligands and isomers involved. transitions are not allowed between orbitals of the same type. the cause for their colour. . consider [Cu(H2O)6]2+ which is a rather pale blue colour vs [Cu(NH3)4]2+ which is an intense dark blue. It is important to remember that the width of many of these peaks is often 1-2000 cm-1 so as long as it is possible to assign peaks unambiguously. Finally. Such transitions often result in a big dipole change for the molecule which is a factor which is associated with a highly probable transition and hence an intense colour. The rule never applies to tetrahedral complexes. Some complexes.
8 Circular dichroism 13. . In the Figure on the left. complementary colors are situated on the opposite sides. Keep in mind that we see the complementary color when visible light of any wavelength is absorbed.9 Electron paramagnetic resonance *Bonding and spectra of M-M bonded compounds 13. a lot of complexes give rise to colorful solutions because of d-d transitions.6 Luminescence 13.7 Spectra of f-block complexes 13.13.10 The ML5 fragment UV spectra As we noticed before.
c) [CrF6]3-. all d-d transitions of centrosymmetric (octahedral) complexes are Laporte forbidden thus weak. Thus.g. b) [Cr(ox)3 ]3-. 2) Spin rule: an allowed transition must not involve a change in the total spin. . no transitions are spin-allowed in a d5 high spin complex.UV spectra from a) [Cr(en)3]3+. (roughly) Selection rules: 1) Laporte: change of parity (g -> u or u -> g) required for an allowed transition. E. υ 1 = ∆o..
10 3 2 4 6 examples [Mn(H2O)6]2+ [Ni(H2O)6]2+ [PdCl4]2six-coordinated complexes of low symmetry metal-ligand CT bands acentric complexes CT bands Splitting by an octahedral field Ground-terms arising from d1 (left) and d2 (right). Correlation and Tanabe-Sugano diagrams . Laporte forbidden Spin allowed.102 102 .10 10 .1 1 .Range of molar absorptivities type of transition Spin and Laporte forbidden Spin allowed.10 10 . Laporte forbidden Spin and Laporte allowed Spin and Laporte allowed Spin and Laporte allowed ε [L mol-1 cm-1 ] 10-3 .103 10 . Laporte forbidden Spin allowed.103 102 .
Correlation diagram for d2 in octahedral ligand field .
transitions 2 Tanabe-Sugano Spin-allowed .diagram for d in octahedral ligand field.
How to favor LMCT: take M with high ionization energy. i. the charge transfer will depend on electron affinities and ionization energies. LMCT. i. Since this resembles an internal redox process. filled orbitals at high energies.e. MLCT ). metal-to-ligand charge transfer. and L with low electron affinity.[M(H2O)6]n+ Charge transfer spectra Charge transfer: Electron transfer from M to L or from L to M.e. an electron moves from a M-based orbital to a L-based orbital or vice versa [ligand-to-metal charge transfer.e. low lying empty d orbitals. Examples are M = . i.
Example for LMCT: MnO4-. like in [Co(H2O)6]3+ and FeI 3. If the d orbitals lie lower than the filled L orbitals.MnVII. L = Se2-. permanganate ion (IUPAC nomenclature??) MO diagram for tetrahedral ML4 showing possible LMCT transitions All four of them are observed experimentally in the case of MnO4 -: L(t1) -> M(e) at 17700 cm-1 (565 nm) L(t1) -> M(t2*) at 29500 cm-1 (340 nm) . I-. PtIV . then a complete internal redox reaction takes place.
red. orange-red. e. BiI3. Further examples: CrO42-: orange. π antibonding orbitals like in CO and pyridine. Example for MLCT: filled M orbitals and empty low lying L orbitals needed. HgI2 . i. PbI2: yellow. MO diagram for octahedral ML6 showing possible MLCT transitions . visible light includes wavelengths between ca.g. 400 and 750 nm. frequencies between 25000 and 13000 cm-1.L(t2) -> M(e) at 30300 cm-1 (330 nm) L(t2) -> M(t2*) at 44400 cm-1 (225 nm) Remember.e. This explains the deep purple color of MnO4( complementary to green).
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