& Comparison With Other Techniques” DIELECTRIC SPECTROSCOPY
• measures the dielectric and electric properties of a medium as a function of frequency (time)
• is based on the interaction of an external electric field with the electric dipole moment and charges of the medium Dielectric properties
Complex dielectric permittivity relative to vacuum
ε*(ω)= ε’(ω)-iε’’(ω)
Complex conductivity σ*(ω)= σ’(ω)+iσ’’(ω)
Complex electric modulus Μ*(ω)=Μ’(ω)+iΜ’’(ω) as a function of temperature Medium in an external electric field ¢ ¢ ¢ ¢ ¢
Electric Field ¡ ¡
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•D= ε0E+P •P= ε χ E 0 s D= ε0εsE •εs= χs+1 Medium in an external electric field
Relation between macroscopic and microscopic quantities
1 P = ∑ pi V i Dipole moments can have an induced or a permanent character
Permanent dipole moments, µ
Induced polarization, P∞
1 N P = ∑ µi + P∞ = µ + P∞ V i V
µ Is determined by: •The interaction between the dipoles •The local electric field at the location of the dipole Medium in an external electric field
Relation between macroscopic and microscopic quantities
•No interaction between dipoles and local electric field equal to the outer applied field thermal energy interaction energy between the dipole and the electric field
µ 2 1 µ 2 N µ = E ε s − ε ∞ = Langevin equation 3kT 3ε 0 kT V
•Interactions between molecules, effect of polarization of environment
2 1 µ N Onsager-Kirkwood-Froehlich equation ε s − ε ∞ = Fg 3ε 0 kT V ε (ε + 2)2 F = s ∞ “Internal field” Onsager factor 3()2ε s + ε ∞ µ 2 g = int = 1+ z cos ψ “Dipole interactions” Kirkwood-Froehlich factor µ 2 Dielectric dispersion in time domain
Perturbation Response Electric Field Electric Displacement E(t) D(t) ε(t)
E(t) D(t)
εεε εεε E 0 s 0 D(t)= ε 0ε (t)E0
ε (t)= ε ∞ + (ε s − ε ∞ )ϕ(t)
ϕ(0)= 0 ϕ(∞)= 1 E εεε εεε E 0 oo0 0
Φ(t)= 1−ϕ(t) 0 t 0 t Dielectric dispersion in frequency domain
Perturbation Response Electric Field Electric Displacement E(ω) D*(ω) ε*(ω)
E(t)=E sin(ϖϖϖt) * 0 D (ω)= D′(ω)+ iD ′′(ω) D(t)=D sin(ϖϖϖt- δδδ) 0 D′(ω)= D0 cos δ (ω)
D′′(ω)= D0 sin δ (ω)