⚛️ Birikmalar katalogi — Mössbauer tahlili
⁵⁷Fe komplekslari · δ (izomer siljish) · ΔEQ (kvadrupol) · Hhf (magnit)
Kompleks birikmalar Mössbauer parametrlari
Ushbu katalog 6 ta klassik ⁵⁷Fe kompleks birikmaning Mössbauer parametrlarini birlashtiradi: izomer siljish δ, kvadrupol bo'linishi ΔEQ, giperkichik magnit maydon Hhf, chiziq kengligi Γ. Har bir birikma uchun elektron konfiguratsiya (dn), term simvoli, koordinatsion simmetriya, spin holati (HS/LS), magnit xossalari, alternativ tahlil usullari va tarixiy kontekst berilgan.
Barcha qiymatlar α-Fe (RT) ga nisbatan mm/s da keltirilgan. Har birikma uchun haroratga bog'liq (T = 4.2, 77, 295 K) parametrlar jadvali mavjud. Manba: peer-reviewed adabiyotlar (Gütlich, Greenwood, Menil).
📈 Katalog statistikasi
Kaliy geksatsianoferrat(III)
« Qizil qon tuzi (Ferricyanide) »
δ
-0.12
mm/s
ΔE_Q
0.28
mm/s
H_hf
0
Tesla
📊 Assimetrik dublet
Γ = 0.28 mm/s
Fe³⁺ (+3)
S = 1/2 (LS)
d⁵ (LS, t₂g⁵ eg⁰)
²T₂g
Oktaedr (O_h, deyarli mukammal)
Paramagnit (μ_eff ≈ 2.25 μB, Kotani egri chizig'i)
Kaliy geksatsianoferrat(II) trigidrat
« Sariq qon tuzi (Ferrocyanide) »
δ
-0.04
mm/s
ΔE_Q
0.00
mm/s
H_hf
0
Tesla
📊 Singlet (deyarli mukammal)
Γ = 0.25 mm/s
Fe²⁺ (+2)
S = 0 (LS)
d⁶ (LS, t₂g⁶ eg⁰)
¹A₁g
Oktaedr (O_h, deyarli ideal)
Diamagnit (χ_M < 0)
Geksaakvatemir(II) ioni
« Temir(II) akvakompleks (och yashil) »
δ
1.39
mm/s
ΔE_Q
3.19
mm/s
H_hf
0
Tesla
📊 Simmetrik dublet (juda katta ΔE_Q)
Γ = 0.3 mm/s
Fe²⁺ (+2)
S = 2 (HS)
d⁶ (HS, t₂g⁴ eg²)
⁵T₂g
Oktaedr (O_h, tri-gonal buzilgan)
Paramagnit (μ_eff = 5.10–5.40 μB, spin+orbital hissa)
Geksaakvatemir(III) ioni
« Temir(III) akvakompleks (och binafsha) »
δ
0.48
mm/s
ΔE_Q
0.15
mm/s
H_hf
0
Tesla
📊 Simmetrik dublet (kichik ΔE_Q, ba'zan singlet ko'rinishida)
Γ = 0.32 mm/s
Fe³⁺ (+3)
S = 5/2 (HS)
d⁵ (HS, t₂g³ eg²)
⁶A₁g
Oktaedr (O_h, deyarli sferik)
Paramagnit (μ_eff = 5.92 μB, spin-only, orbital hissa nol)
Pentakarboniltemir(0)
« Temir pentakarbonil (Mond-Berthelot suyuqligi) »
δ
-0.09
mm/s
ΔE_Q
2.57
mm/s
H_hf
0
Tesla
📊 Assimetrik dublet (katta ΔE_Q, past δ)
Γ = 0.26 mm/s
Fe⁰ (0)
S = 0
d⁸ (18e⁻ ko'rinishida yopiq qobiq)
¹A₁' (D₃ₕ)
Trigonal-bipiramidal (D₃ₕ)
Diamagnit
Temir(II,III) oksidi
« Magnetit (mineral), lodestone »
δ
0.28
mm/s
ΔE_Q
0.00
mm/s
H_hf
49.0
Tesla
📊 Ikki sekstet (A + B) — RT da; past T da uch sekstet (Verwey pastida)
Γ = 0.3 mm/s
Fe³⁺ (A) + [Fe²⁺, Fe³⁺] (B) (+2, +3 (aralash))
A: S=5/2 ↓ | B: S=5/2, S=2 ↑ (antiparalel — ferrimagnit)
Fe(A)³⁺: d⁵ HS · Fe(B)²⁺: d⁶ HS · Fe(B)³⁺: d⁵ HS
⁶A₁g (A), ⁵T₂g (B, Fe²⁺), ⁶A₁g (B, Fe³⁺)
Tetraedrik (A-sayt) + Oktaedrik (B-sayt)
Ferrimagnit (T_C = 858 K, M_s = 92 emu/g, RT da)
📊 δ vs ΔEQ — Fe holatlari xaritasi
Har bir nuqta — birikma. Mintaqalar Fe oksidlanish darajasi va spin holatining tipik parametrlar oralig'i.
📋 Tayanch jadval — Fe holatlarining tipik Mössbauer parametrlari
Barcha qiymatlar α-Fe (RT) ga nisbatan, T = 295 K uchun tipik.
| Elektron holat | δ (mm/s) | ΔE_Q (mm/s) | Spektr shakli | Tipik misol |
|---|---|---|---|---|
| Fe(0), d⁸ (18e⁻) | −0.20 ÷ +0.05 | 0.0 ÷ 2.6 | Singlet / dublet | [Fe(CO)₅] |
| Fe(II) LS, t₂g⁶ | −0.10 ÷ +0.50 | 0.0 ÷ 1.0 | Singlet | K₄[Fe(CN)₆] |
| Fe(II) HS, t₂g⁴eg² | +0.90 ÷ +1.50 | 2.0 ÷ 3.5 | Katta dublet | [Fe(H₂O)₆]²⁺ |
| Fe(III) LS, t₂g⁵ | −0.15 ÷ +0.30 | 0.4 ÷ 3.0 | Dublet | K₃[Fe(CN)₆] |
| Fe(III) HS, d⁵ | +0.30 ÷ +0.60 | 0.0 ÷ 0.8 | Kichik dublet | [Fe(H₂O)₆]³⁺ |
| Aralash Fe²⁺/Fe³⁺ | ikki komponent | har xil | Ikki sekstet + H_hf | Fe₃O₄ |
💡 Manba: Gütlich, Bill, Trautwein (2011); Greenwood & Gibb (1971); Menil (1985). Aniq qiymatlar ligand maydonining kuchi (spektrokimyoviy qator), koordinatsion soni, kristall panjarasi va haroratga bog'liq — jadval faqat tayanch ma'lumot beradi.
🔬 Nima uchun aynan bu 6 ta birikma?
1️⃣ K₃[Fe(CN)₆] — Fe(III) LS
Kuchli maydon CN⁻ ning ta'siri, LS holatning klassik dublet spektri va manfiy δ ning misoli.
2️⃣ K₄[Fe(CN)₆] — Fe(II) LS
t₂g⁶ sferik simmetriya ⇒ ΔE_Q = 0 ning mukammal namunasi. Singletning oltin standarti.
3️⃣ [Fe(H₂O)₆]²⁺ — Fe(II) HS
t₂g⁴eg² ning katta EFG i, δ~1.4, ΔE_Q~3.2 — d-elektron asimmetriyaning maksimal ta'siri.
4️⃣ [Fe(H₂O)₆]³⁺ — Fe(III) HS
d⁵ yarim-to'lgan holat, sferik simmetriya, kichik ΔE_Q — Fe(III) HS ning yetakchi mezoni.
5️⃣ [Fe(CO)₅] — Fe(0) 18e⁻
Ekstremal past δ (π-back-bonding), D₃ₕ simmetriya intrinsik ΔE_Q beradi. Metallorganik klassik.
6️⃣ Fe₃O₄ — Aralash valent
Ferrimagnit sekstet, ikki (RT) yoki uch (Verwey pastida) komponent, H_hf ~49 T. Xoreografik.
📚 Manba adabiyotlar
- P. Gütlich, E. Bill, A. X. Trautwein — Mössbauer Spectroscopy and Transition Metal Chemistry: Fundamentals and Applications. Springer, 2011.
- N. N. Greenwood, T. C. Gibb — Mössbauer Spectroscopy. Chapman & Hall, London, 1971 (klassik ma'lumotnoma).
- F. Menil — Systematic trends of the ⁵⁷Fe Mössbauer isomer shifts. J. Phys. Chem. Solids 46, 763 (1985).
- G. J. Long (ed.) — Mössbauer Spectroscopy Applied to Inorganic Chemistry, Vol. 1–3, Plenum Press.
- M. D. Dyar, D. G. Agresti et al. — Mössbauer spectroscopy of Earth and planetary materials. Ann. Rev. Earth Planet. Sci. 34, 83 (2006).
- R. H. Herber (ed.) — Chemical Mössbauer Spectroscopy. Plenum Press, 1984.
- G. Klingelhöfer et al. — MIMOS-II Mars Rover Mössbauer results. J. Geophys. Res. 108, 8067 (2003).