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Catégorie :Category: nCreator TI-Nspire
Auteur Author: Meronjeb
Type : Classeur 3.0.1
Page(s) : 1
Taille Size: 4.89 Ko KB
Mis en ligne Uploaded: 17/12/2024 - 18:20:13
Uploadeur Uploader: Meronjeb (Profil)
Téléchargements Downloads: 3
Visibilité Visibility: Archive publique
Shortlink : http://ti-pla.net/a4415426
Type : Classeur 3.0.1
Page(s) : 1
Taille Size: 4.89 Ko KB
Mis en ligne Uploaded: 17/12/2024 - 18:20:13
Uploadeur Uploader: Meronjeb (Profil)
Téléchargements Downloads: 3
Visibilité Visibility: Archive publique
Shortlink : http://ti-pla.net/a4415426
Description
Fichier Nspire généré sur TI-Planet.org.
Compatible OS 3.0 et ultérieurs.
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Absorbance: A=ebc, e=molar absorptivity in L/mol*cm. Metals have weak absorption (pale color) if no excited states with the same spin multiplicity as the ground state and hence no allowed d-d transitions (Mn at d5). The Zn complex has filled t2g and eg* orbitals, so no d-d transitions are possible (d10). I0 is the light that enters and I is the light that leaves. I=0.8Io means 80% light was transmitted, 20% absorbed. Microstates: i=# of possible combinations of ml and ms for an individual electron (d=10) j=# of electrons (ml^spin,ms^spin), (1+,0+)=(0+,1+). (1+,1+) violates Pauli-exclusion principle - 6!-1!=5!. For two different orbitals, multiply the total MS for each to yield total. TABLE: Find array. Find L and S for each array. Derive the term symbol L=1 (P). Multiplicity=(2S+1)=n+1, n=unpaired e-s. Ground state: (drawing MS with max M and S will be GS) Largest S Tie, Largest L -Also, Spin orbiting coupling (J). Much smaller than Russel Saunders coupling. J=(L+S), L+S-1,...I(L-S)l. -Causes states to split. For less than 1.2 filled subshell, the lowest J value is GS. For more than half-filled, the Highest J-value is GS. -MS on top from left - to + right. ML on side from positive up to negative down. Q#s + Coupling Each e- has a magnetic field from orbital movement, and spin. Allowing Magnetic fields of the electrons from the orbitals to interact (ML), and the magnetic fields of the e-s from the spin (MS). Electron pairs (see) each other causing Russel-Saunders coupling. d1: 2D d2: 1S 1D 1G, 3P 3F d3: 2D, 4P 4F, 2P 2D 2F 2G 2H d4: 5D, 1S 1D 1G, 3P 3F, 3P 3D 3F 3G 3H, 1S 1D 1F 1G 1I d5: 2D, 4P 4F, 2P 2D 2F 2G 2H, 2S 2D 2F 2G 2I, 4D 4G, 6S d6: Same as d4 d7: Same as d3 d8: Same as d2 d9: Same as d1 d10: 1S Ligand effects: T2G stabilizes w/ stronger ligand field while eg* destabilizes. Smal energy diff that increases w/ stronger LF b/c upper eg* orbitals raise in energy as T2g lower orbitals decrease. Delta0 increases w/ increasing Ligand field. When Delta0 is very large (with infinite strong ligands), interactions between electrons (russel sounders coupling) is negligible. All that matters is if the electrons belong to T2g or eg*. Selection Rules for Electronic Transitions: 1. Spin Selection Rule: Transitions between states w/ different spin multiplicities are forbidden. One triplet state can access another triplet state. If electrons are paired with each other in one state, the electrons cannot flip to go to another 2. Laporte Selection Rule: A molecule with inversion symmetry cannot undergo d->d transitions. Td doesnt have inversion symmetry while Octahedral does. Breaking LaPortes rule 1. All Ligands are not identical (lose inversion symmetry) 2. T2g -> eg* are not pure d orbitals (have ligand sigma and metal d orbital components). Pure d-d transitions are not allowed. 3. If in a molecule where all ligands are the same, this rule can be broken via an asymmetric vibration. Electronic transition can couple to this transition. Fibrotic coupling is possible. A vibration can destroy the inversion symmetry. Term Symbol After Oh: T: unequally occupied triply degenerate orbitals E: unequally occupied doubly degenerate orbitals A: no unequally occupied degenerate orbitals Superscript: n+1 Tanabe-Subano Diagrams: - Horizontal line=ground state - Left is no Ligand Field, Right is strong Ligand field. - If same term symbol, no-crossing rule, therefore bowing in lines. - If exists a line in the middle, left is hi spin ligand (F-), right low spin ligand (CO). - JT distortions. Most common w/ d9. Weaker interaction= less AB* overlap=less energy. Changes molecule symmetry. d1-d9 2D terms inverted d2-d8 3F terms inverted d3-d7 (hi) 4f terms inverted d4-d6 (hi) 5D terms inverted - d1, d3, d4(hi spin), d6(lo spin), d8, d9 First transition is delta0. - d2, d7 (hi spin), find v2/v1, delta0/B, go to value on TS diagram and find E/B values at deltao/B value, find avg B value (E is absorption band), find avg Delta 0 Charge Transfer: MLCT: Metal to Ligand CT. Md to Lpi* (Oxidation of metal) LMCT: Ligand to Metal CT. Lsigma or pi MOs to Md. (reduction of metal). F-ligands have filled sigma and p orbitals (no empty pi* orbitals) that can transfer electrons into empty/half-filled d orbitals - Delta0=Transfer from( L to eg*) - (L to T2g) when d shell is unfilled - The metal-to-ligand charge transfer (MLCT) excites an electron from a filled metal d-orbital to an empty À* orbital on CO. As the metal's oxidation state increases, its d-orbitals are drawn to lower energy, causing the MLCT band to increase in energy. - High intensity (large A and e) is charge transfer while low intensity (small A and e) is d-d transition. Luminescence/decay: - Fluorescence: Radiative decay from an excited state w/ the same multiplicity as the ground state. - Phosphorescence: Radiative decay from an excited state w/ a different multiplicity as the ground state. Occur via ISC. It lasts much longer as it breaks the spin-selection rule. d3:4T1 t
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Compatible OS 3.0 et ultérieurs.
<<
Absorbance: A=ebc, e=molar absorptivity in L/mol*cm. Metals have weak absorption (pale color) if no excited states with the same spin multiplicity as the ground state and hence no allowed d-d transitions (Mn at d5). The Zn complex has filled t2g and eg* orbitals, so no d-d transitions are possible (d10). I0 is the light that enters and I is the light that leaves. I=0.8Io means 80% light was transmitted, 20% absorbed. Microstates: i=# of possible combinations of ml and ms for an individual electron (d=10) j=# of electrons (ml^spin,ms^spin), (1+,0+)=(0+,1+). (1+,1+) violates Pauli-exclusion principle - 6!-1!=5!. For two different orbitals, multiply the total MS for each to yield total. TABLE: Find array. Find L and S for each array. Derive the term symbol L=1 (P). Multiplicity=(2S+1)=n+1, n=unpaired e-s. Ground state: (drawing MS with max M and S will be GS) Largest S Tie, Largest L -Also, Spin orbiting coupling (J). Much smaller than Russel Saunders coupling. J=(L+S), L+S-1,...I(L-S)l. -Causes states to split. For less than 1.2 filled subshell, the lowest J value is GS. For more than half-filled, the Highest J-value is GS. -MS on top from left - to + right. ML on side from positive up to negative down. Q#s + Coupling Each e- has a magnetic field from orbital movement, and spin. Allowing Magnetic fields of the electrons from the orbitals to interact (ML), and the magnetic fields of the e-s from the spin (MS). Electron pairs (see) each other causing Russel-Saunders coupling. d1: 2D d2: 1S 1D 1G, 3P 3F d3: 2D, 4P 4F, 2P 2D 2F 2G 2H d4: 5D, 1S 1D 1G, 3P 3F, 3P 3D 3F 3G 3H, 1S 1D 1F 1G 1I d5: 2D, 4P 4F, 2P 2D 2F 2G 2H, 2S 2D 2F 2G 2I, 4D 4G, 6S d6: Same as d4 d7: Same as d3 d8: Same as d2 d9: Same as d1 d10: 1S Ligand effects: T2G stabilizes w/ stronger ligand field while eg* destabilizes. Smal energy diff that increases w/ stronger LF b/c upper eg* orbitals raise in energy as T2g lower orbitals decrease. Delta0 increases w/ increasing Ligand field. When Delta0 is very large (with infinite strong ligands), interactions between electrons (russel sounders coupling) is negligible. All that matters is if the electrons belong to T2g or eg*. Selection Rules for Electronic Transitions: 1. Spin Selection Rule: Transitions between states w/ different spin multiplicities are forbidden. One triplet state can access another triplet state. If electrons are paired with each other in one state, the electrons cannot flip to go to another 2. Laporte Selection Rule: A molecule with inversion symmetry cannot undergo d->d transitions. Td doesnt have inversion symmetry while Octahedral does. Breaking LaPortes rule 1. All Ligands are not identical (lose inversion symmetry) 2. T2g -> eg* are not pure d orbitals (have ligand sigma and metal d orbital components). Pure d-d transitions are not allowed. 3. If in a molecule where all ligands are the same, this rule can be broken via an asymmetric vibration. Electronic transition can couple to this transition. Fibrotic coupling is possible. A vibration can destroy the inversion symmetry. Term Symbol After Oh: T: unequally occupied triply degenerate orbitals E: unequally occupied doubly degenerate orbitals A: no unequally occupied degenerate orbitals Superscript: n+1 Tanabe-Subano Diagrams: - Horizontal line=ground state - Left is no Ligand Field, Right is strong Ligand field. - If same term symbol, no-crossing rule, therefore bowing in lines. - If exists a line in the middle, left is hi spin ligand (F-), right low spin ligand (CO). - JT distortions. Most common w/ d9. Weaker interaction= less AB* overlap=less energy. Changes molecule symmetry. d1-d9 2D terms inverted d2-d8 3F terms inverted d3-d7 (hi) 4f terms inverted d4-d6 (hi) 5D terms inverted - d1, d3, d4(hi spin), d6(lo spin), d8, d9 First transition is delta0. - d2, d7 (hi spin), find v2/v1, delta0/B, go to value on TS diagram and find E/B values at deltao/B value, find avg B value (E is absorption band), find avg Delta 0 Charge Transfer: MLCT: Metal to Ligand CT. Md to Lpi* (Oxidation of metal) LMCT: Ligand to Metal CT. Lsigma or pi MOs to Md. (reduction of metal). F-ligands have filled sigma and p orbitals (no empty pi* orbitals) that can transfer electrons into empty/half-filled d orbitals - Delta0=Transfer from( L to eg*) - (L to T2g) when d shell is unfilled - The metal-to-ligand charge transfer (MLCT) excites an electron from a filled metal d-orbital to an empty À* orbital on CO. As the metal's oxidation state increases, its d-orbitals are drawn to lower energy, causing the MLCT band to increase in energy. - High intensity (large A and e) is charge transfer while low intensity (small A and e) is d-d transition. Luminescence/decay: - Fluorescence: Radiative decay from an excited state w/ the same multiplicity as the ground state. - Phosphorescence: Radiative decay from an excited state w/ a different multiplicity as the ground state. Occur via ISC. It lasts much longer as it breaks the spin-selection rule. d3:4T1 t
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