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Tom Ziegler Department of Chemistry University of Calgary,Alberta, Canada T2N 1N4
Magnetically Perturbed Time Dependent Density Functional Theory.Applications and Implementations
Tuesday November 11 11:30 am - 12:10 pm
ADF• Solves Kohn-Sham equations• Properties
– NMR, EFG, EPR, Raman, IR, UV/Vis, NLO, CD, …– Potential energy surfaces (transition states, geometry
optimization)• Environment effects
– QM/MM, COSMO• Relativistic effects
– Scalar relativistic effects, spin-orbit coupling– Transition and heavy metal compounds
• Uses Slater functions
hv
Cl
C
C
C
C
C
Si Zr
C
C
C
C
Cl
C
Inorganic SpectroscopyInorganic Spectroscopy
Basic Time Dependent Density Functionl TheoryBasic Time Dependent Density Functionl Theory
Basic Equation :Basic Equation :
€
Aia, jb = (εa − εi)0δ ijδab +∂F ia
∂Pjb
⎛
⎝ ⎜ ⎜
⎞
⎠ ⎟ ⎟0
€
Bia,bj =∂F ia
∂Pbj
⎛
⎝ ⎜ ⎜
⎞
⎠ ⎟ ⎟0
Definition of A and B Matrices :Definition of A and B Matrices :
M.E.CasidaM.E.Casida
Gross,E.K.; Kohn W.Gross,E.K.; Kohn W.
€
ΩF (λ ) =Wλ2F (λ )
€
Ω=−S−1/2(A + B)S−1/2
€
S−1/ 2 = (A − B)1/ 2
Where :Where :
T. Ziegler,M.Seth,M.Krykunov,J.AutschbachA Revised Electronic Hessian for Approximate Time-Dependent Density Functional TheorySUBMITTED, J.C.P.
T. Ziegler,M.Seth,M.Krykunov,J.AutschbachA Revised Electronic Hessian for Approximate Time-Dependent Density Functional TheorySUBMITTED, J.C.P.
Basic Time Dependent Density Functionl TheoryBasic Time Dependent Density Functionl Theory
Basic Equation :Basic Equation :
€
Aia, jb = (εa − εi)0δ ijδab +∂F ia
∂Pjb
⎛
⎝ ⎜ ⎜
⎞
⎠ ⎟ ⎟0
€
Bia,bj =∂F ia
∂Pbj
⎛
⎝ ⎜ ⎜
⎞
⎠ ⎟ ⎟0
Corredted Definition of A and B Matrices :Corredted Definition of A and B Matrices :
M.E.CasidaM.E.Casida
Gross,E.K.; Kohn W.Gross,E.K.; Kohn W.
€
ΩF (λ ) =Wλ2F (λ )
€
Ω=−S−1/2(A + B)S−1/2
€
S−1/ 2 = (A − B)1/ 2
Where :Where :
€
+ f1
2[Jaa,aa − Kaa,aa + Jii,ii − K ii,ii − 2Jaa,ii + 2Kaa,ii]
€
+ f1
2[Jaa,aa − Kaa,aa + Jii,ii − K ii,ii − 2Jaa,ii + 2Kaa,ii]
Basic Time Dependent Density Functionl TheoryBasic Time Dependent Density Functionl Theory
Basic Equation :Basic Equation :
€
Aia, jb = (εa − εi)0δ ijδab +∂F ia
∂Pjb
⎛
⎝ ⎜ ⎜
⎞
⎠ ⎟ ⎟0
€
Bia,bj =∂F ia
∂Pbj
⎛
⎝ ⎜ ⎜
⎞
⎠ ⎟ ⎟0
Corredted Definition of A and B Matrices :Corredted Definition of A and B Matrices :
M.E.CasidaM.E.Casida
Gross,E.K.; Kohn W.Gross,E.K.; Kohn W.
€
ΩF (λ ) =Wλ2F (λ )
€
Ω=−S−1/2(A + B)S−1/2
€
S−1/ 2 = (A − B)1/ 2
Where :Where :
Spin-flip transitions using non-collinear functionalsLiu (2004),Ziegler+Wang (2005),Vahtras (2007)
Basic Time Dependent Density Functionl TheoryBasic Time Dependent Density Functionl Theory
€
Wλ = ΔE o,λTransition Energy :Transition Energy :
Basic Equation :Basic Equation :M.E.CasidaM.E.Casida
Gross,E.K.; Kohn W.Gross,E.K.; Kohn W.
€
ΩF (λ ) = Wλ2F (λ )
Electric Transition Dipole Moment :Electric Transition Dipole Moment :
€
Aα ˆ M Jλ =1
WJ
μ iaFia(Jλ ) (εa − εi)
ia
∑
€
μ ia = − ir r a
€
Jλ ˆ L Aα = WJ liaFia( Jλ ) 1
(ε a −ε i )ia
∑
Magnetic Transition Dipole Moment :Magnetic Transition Dipole Moment :
€
l jb = −iμB jr r ×
r ∇ b
A
C
B
A
B
C
Absorption Spectra and TD-DFTAbsorption Spectra and TD-DFT
Transition Energy :Transition Energy :
€
fλ =2
3μ iaFia
(Jλ ) (εa − εi)ia
∑ ⎡
⎣ ⎢
⎤
⎦ ⎥⋅ μ jbF jb
(Jλ ) (εb − ε j )jb
∑∫ ⎡
⎣ ⎢ ⎢
⎤
⎦ ⎥ ⎥
€
Wλ = ΔE0,λ
hv
Cl
C
C
C
C
C
Si Zr
C
C
C
C
Cl
C
Inorganic SpectroscopyInorganic Spectroscopy
N
MN N
N
H
Why MCD and MOR ? Why MCD and MOR ?
Magnetic Circular Dichroism (MCD) SpectroscopyMagnetic Circular Dichroism (MCD) Spectroscopy
More information about each excited stateMore information about each excited state
In absorption spectroscopy onlypositive (often overlapping) bandsIn absorption spectroscopy onlypositive (often overlapping) bands
Why MCD ? Why MCD ?
Magnetic Circular Dichroism (MCD) SpectroscopyMagnetic Circular Dichroism (MCD) Spectroscopy
In MCD bands of different shapesMore information about each excited stateIn MCD bands of different shapesMore information about each excited state
Magnetic Circular Dichroism (MCD) SpectroscopyMagnetic Circular Dichroism (MCD) Spectroscopy
€ €
Origin of MCD ? Origin of MCD ?
€
AJ = γoω(NAαg − N Jλ j )
Nαλgj∑ Aαg ˆ M Jλ j
2 ⎛ ⎝ ⎜ ⎞
⎠ ⎟× ρ Aαg.Jλ j (ω)
€
AJ = γoω(NAαg − N Jλ j )
Nαλgj∑ Aαg ˆ M Jλ j
2 ⎛ ⎝ ⎜ ⎞
⎠ ⎟× ρ Aαg.Jλ j (ω)
Electric dipole operator:Electric dipole operator:
€
ˆ M = ˆ m ii∑ = − (xii
∑ r e xi
+ yi
r e yi
+ yi
r e yi
)
€
ˆ M = ˆ m ii∑ = − (xii
∑ r e xi
+ yi
r e yi
+ yi
r e yi
)
Absorbance in dipole approximation.Absorbance in dipole approximation.
Aα
Jλ
Magnetic Circular Dichroism (MCD) SpectroscopyMagnetic Circular Dichroism (MCD) Spectroscopy
€ €
Origin of MCD ? Origin of MCD ?
€
AJ = γoω(NAαg − N Jλ j )
Nαλgj∑ Aαg ˆ M Jλ j
2 ⎛ ⎝ ⎜ ⎞
⎠ ⎟× ρ Aαg.Jλ j (ω)
€
AJ = γoω(NAαg − N Jλ j )
Nαλgj∑ Aαg ˆ M Jλ j
2 ⎛ ⎝ ⎜ ⎞
⎠ ⎟× ρ Aαg.Jλ j (ω)
Absorbance in dipole approximation.Absorbance in dipole approximation.
Aα
Jλ
€
ρAαg.Jλj (ω) ≈ fJ (ω −ωJλ ) =1
πWJ
e−
ωJλ −ω
WJ
⎛
⎝ ⎜
⎞
⎠ ⎟
2
Magnetic Circular Dichroism (MCD) SpectroscopyMagnetic Circular Dichroism (MCD) Spectroscopy
Electric dipole operatorFor circular polarizedLight:
Electric dipole operatorFor circular polarizedLight:
€
ˆ M ± = ˆ m ±,ii∑
€
ˆ M ± = ˆ m ±,ii∑€
ΔAJ
ω= γo
(NAαg − N Jλj )
Nαλgj∑ Aαg ˆ M − Jλ j
2− Aαg ˆ M + Jλ j
2 ⎛ ⎝ ⎜ ⎞
⎠ ⎟× ρ Aαg.Jλ j (ω)
Difference in absorbance of left and right circular polarized lightDifference in absorbance of left and right circular polarized light
Circular Polarized LightCircular Polarized Light
€
ˆ m − =1
2(x
r e x − iy
r e y )
€
ˆ m + =1
2(x
r e x + iy
r e y )
Origin of MCD ? Origin of MCD ?
Magnetic Circular Dichroism (MCD) SpectroscopyMagnetic Circular Dichroism (MCD) Spectroscopy
€
ΔAJ'
ω=
A−,J'
ω−
A+,J'
ω
γo
(NAαg − N Jλj )
Nαλgj∑ Aαg ˆ M − Jλ j
2− Aαg ˆ M + Jλ j
2 ⎛ ⎝ ⎜ ⎞
⎠ ⎟.ρ Aαg.Jλ j (ω)
⎛
⎝ ⎜
⎞
⎠ ⎟
'
The difference in absorption of left and right circularly polarized light in the presence of a magnetic field as a function of photon energy
The difference in absorption of left and right circularly polarized light in the presence of a magnetic field as a function of photon energy
Origin of MCD ? Origin of MCD ?
€
ρAαg.Jλj (ω) ≈ fJ (ω −ωJλ, ) =
1
π WJ
e−
ω Jλ, −ω
WJ
⎛
⎝ ⎜ ⎜
⎞
⎠ ⎟ ⎟
2
Magnetic Circular Dichroism (MCD) SpectroscopyMagnetic Circular Dichroism (MCD) Spectroscopy
€
ΔAJ'
hω=
γo
3 γ
3
∑ (NAα − N Jλ )
Nαλ∑ Aα ˆ M −
γ Jλ2
− Aα ˆ M +γ Jλ
2 ⎛ ⎝ ⎜ ⎞
⎠ ⎟ ∂
∂Bγ
fJ (ω −ωJλ )( )oB
+γo
3 γ
3
∑ (NAα − N Jλ )
Nαλ∑ ∂
∂Bγ
Aα ˆ M −γ Jλ
2− Aα ˆ M +
γ Jλ2 ⎛
⎝ ⎜ ⎞
⎠ ⎟o
fJ (ω −ωJ )B
+γo
3
∂
∂B γ
3
∑ (NAα − N J )
N
⎛
⎝ ⎜
⎞
⎠ ⎟o
α∑ Aα ˆ M −
γ Jλ2
− Aα ˆ M +γ Jλ
2 ⎛ ⎝ ⎜ ⎞
⎠ ⎟ fJ (ω −ωJ )B
€
ΔAJ'
hω=
γo
3 γ
3
∑ (NAα − N Jλ )
Nαλ∑ Aα ˆ M −
γ Jλ2
− Aα ˆ M +γ Jλ
2 ⎛ ⎝ ⎜ ⎞
⎠ ⎟ ∂
∂Bγ
fJ (ω −ωJλ )( )oB
+γo
3 γ
3
∑ (NAα − N Jλ )
Nαλ∑ ∂
∂Bγ
Aα ˆ M −γ Jλ
2− Aα ˆ M +
γ Jλ2 ⎛
⎝ ⎜ ⎞
⎠ ⎟o
fJ (ω −ωJ )B
+γo
3
∂
∂B γ
3
∑ (NAα − N J )
N
⎛
⎝ ⎜
⎞
⎠ ⎟o
α∑ Aα ˆ M −
γ Jλ2
− Aα ˆ M +γ Jλ
2 ⎛ ⎝ ⎜ ⎞
⎠ ⎟ fJ (ω −ωJ )B
€
ΔAJ'
ω= −γoA J
∂fJ (ω −ωJ )
∂ωB +γ0B J fJ (ω −ωJ )B +γoC J fJ (ω −ωJ )B
€
ΔAJ'
ω= −γoA J
∂fJ (ω −ωJ )
∂ωB +γ0B J fJ (ω −ωJ )B +γoC J fJ (ω −ωJ )B
Origin of MCD ? Origin of MCD ?
€
ΔAJ'
ω= −γoA J
∂fJ (ω −ωJ )
∂ωB +γ0B J fJ (ω −ωJ )B
+γoC J fJ (ω −ωJ )B
€
ΔAJ'
ω= −γoA J
∂fJ (ω −ωJ )
∂ωB +γ0B J fJ (ω −ωJ )B
+γoC J fJ (ω −ωJ )B
Magnetic Circular Dichroism (MCD) SpectroscopyMagnetic Circular Dichroism (MCD) Spectroscopy
The MCD disprsion The MCD disprsion
P.J.Stephens. Ph.D. Thesis 1964
A
B
C(T)
A
€
ΔAJ'
ω= −γoA J
∂fJ (ω −ωJ )
∂ωB +γ0B J fJ (ω −ωJ )B
+γoC J fJ (ω −ωJ )B
€
ΔAJ'
ω= −γoA J
∂fJ (ω −ωJ )
∂ωB +γ0B J fJ (ω −ωJ )B
+γoC J fJ (ω −ωJ )B
Magnetic Circular Dichroism (MCD) SpectroscopyMagnetic Circular Dichroism (MCD) Spectroscopy
The MCD disprsion The MCD disprsion
P.J.Stephens. Ph.D. Thesis 1964
Positive A-term
Absorption band Negative A-term
Degenerate ground- or (and) excited state
€
ΔAJ'
ω= −γoA J
∂fJ (ω −ωJ )
∂ωB +γ0B J fJ (ω −ωJ )B
+γoC J fJ (ω −ωJ )B
€
ΔAJ'
ω= −γoA J
∂fJ (ω −ωJ )
∂ωB +γ0B J fJ (ω −ωJ )B
+γoC J fJ (ω −ωJ )B
Magnetic Circular Dichroism (MCD) SpectroscopyMagnetic Circular Dichroism (MCD) Spectroscopy
The MCD disprsion The MCD disprsion
P.J.Stephens. Ph.D. Thesis 1964
Absorption band
All cases
Negative B-term
Positive B-term
Negative B-term
Positive B-term
€
ΔAJ'
ω= −γoA J
∂fJ (ω −ωJ )
∂ωB +γ0B J fJ (ω −ωJ )B
+γoC J fJ (ω −ωJ )B
€
ΔAJ'
ω= −γoA J
∂fJ (ω −ωJ )
∂ωB +γ0B J fJ (ω −ωJ )B
+γoC J fJ (ω −ωJ )B
Magnetic Circular Dichroism (MCD) SpectroscopyMagnetic Circular Dichroism (MCD) Spectroscopy
The MCD disprsion The MCD disprsion
P.J.Stephens. Ph.D. Thesis 1964
Absorption band
Space and(or) spin-degenerate ground state
Negative C-term
Positive C-term
Origin of B-TermOrigin of B-Term
The B term The B term
O
X+iaY
Y-iaX
M- M+
B>0
ΔA-A+
A-
B>0
O
X
Y
M- M+
B=0
-A+
A-ΔA
B=0
€
ΔA '
ω= γoB -A J
∂fJ (ω −ωJ )B
∂ω+(B J +
C J
kT) fJ (ω −ωJ )B
⎡
⎣ ⎢ ⎤
⎦ ⎥J∑
€
ΔA '
ω= γoB -A J
∂fJ (ω −ωJ )B
∂ω+(B J +
C J
kT) fJ (ω −ωJ )B
⎡
⎣ ⎢ ⎤
⎦ ⎥J∑
€
B J =1
3 γ
3
∑λ
∑ ∂
∂Bγ
Aα ˆ M −γ Jλ
2− Aα ˆ M +
γ Jλ2 ⎛
⎝ ⎜ ⎞
⎠ ⎟o
M.Seth,T.Ziegler, M.Krykunov, J.Autschbach J.Chem.Phys. J. Chem. Phys. 128, 144105 (2008)
Expression for the B-TermExpression for the B-Term
The B term The B term
€
B J =1
3 γ
3
∑λ
∑ ∂
∂Bγ
Aα ˆ M −γ Jλ
2− Aα ˆ M +
γ Jλ2 ⎛
⎝ ⎜ ⎞
⎠ ⎟o
Or by using the identity Or by using the identity
€
t
∑ A ˆ M t J2
− A ˆ M t J2
= i ε rst
r,s ,t
∑ A ˆ M r J J ˆ M s A = i ε rst
r ,s,t
∑ α rs (ωL )
€
Here ε rst is the three - dimensional Levi - Civita symbol
€
Here ε rst is the three - dimensional Levi - Civita symbol
We thus haveWe thus have
€
BJ =i
3 s,t ,u
3
∑ εstu
∂α st (ω)
∂Bu
⎛
⎝ ⎜
⎞
⎠ ⎟ω=ωL( )
M.Seth,T.Ziegler, M.Krykunov, J.Autschbach J.Chem.Phys. J. Chem. Phys. 128, 144105 (2008)
The Calculation of the B-termThe Calculation of the B-term
The B term : practical calculations The B term : practical calculations
We have:We have:
TD-DFT calculationsTD-DFT calculations
€
€
B J =i
3ε stu
∂α st (ω)
∂Bu
⎛
⎝ ⎜
⎞
⎠ ⎟
s,t ,u
∑ω=ωL
Where:Where:
€
α st (ω)ω=ωL= m s[XL (ω) + YL (ω)][m t (XL (ω) + YL (ω)]
€
ωC 0
0 −C
⎛
⎝ ⎜
⎞
⎠ ⎟X
Y
⎛
⎝ ⎜
⎞
⎠ ⎟=
A B
B* A*
⎛
⎝ ⎜
⎞
⎠ ⎟X
Y
⎛
⎝ ⎜
⎞
⎠ ⎟
Early work:
J.Michl, J.Am.Chem.Soc. 100,6801 (1978)
Early work:
J.Michl, J.Am.Chem.Soc. 100,6801 (1978)
€
m s = i(0) m s a(0)
The B term : practical calculations The B term : practical calculations
We have:We have:
TD-DFT calculationsTD-DFT calculations
Solve:
€
€
BJ = −i
3εstu
∂α st (ω)
∂Bu
⎛
⎝ ⎜
⎞
⎠ ⎟
s,t ,u
∑ω=ωL
Where:Where:
€
ω(0) C 0
0 −C
⎛
⎝ ⎜
⎞
⎠ ⎟X (0)
Y (0)
⎛
⎝ ⎜
⎞
⎠ ⎟=
A(0) B(0)
B(0) A(0)
⎛
⎝ ⎜
⎞
⎠ ⎟X (0)
Y (0)
⎛
⎝ ⎜
⎞
⎠ ⎟
€
BAJ = −2i
3εstu[
stu
∑ m s(1)u(XJ(0) −YJ
(0))m t(0)(XJ(0) + YJ
(0))
+m s(0)(XJ(1)u + YJ
(1)u)m t(0)(XJ(0) + YJ
(0))]
The Calculation of the B-termThe Calculation of the B-term
The B term : practical calculations The B term : practical calculations
By differentiation ofBy differentiation of
€
ω(0) C 0
0 −C
⎛
⎝ ⎜
⎞
⎠ ⎟X (0)
Y (0)
⎛
⎝ ⎜
⎞
⎠ ⎟=
A(0) B(0)
B(0) A(0)
⎛
⎝ ⎜
⎞
⎠ ⎟X (0)
Y (0)
⎛
⎝ ⎜
⎞
⎠ ⎟
€
Implementation - X(1), Y(1)( )
€
The equation that we use for evaluating (X(1), Y(1) ) is
€
A(0) B(0)
B(0)* A(0)*
⎛
⎝ ⎜
⎞
⎠ ⎟−ωI
(0) −I 0
0 I
⎛
⎝ ⎜
⎞
⎠ ⎟
⎛
⎝ ⎜ ⎜
⎞
⎠ ⎟ ⎟X I
(1)
YI(1)
⎛
⎝ ⎜
⎞
⎠ ⎟=
ωI(1) −I 0
0 I
⎛
⎝ ⎜
⎞
⎠ ⎟−
A(1) B(1)
B(1)* A(1)*
⎛
⎝ ⎜
⎞
⎠ ⎟
⎛
⎝ ⎜ ⎜
⎞
⎠ ⎟ ⎟X I
(0)
YI(0)
⎛
⎝ ⎜
⎞
⎠ ⎟
The Calculation of the B-termThe Calculation of the B-term
€
BAJ = −2i
3εstu[
stu
∑ m s(1)u(XJ(0) −YJ
(0))m t(0)(XJ(0) + YJ
(0))
+m s(0)(XJ(1)u + YJ
(1)u)m t(0)(XJ(0) + YJ
(0))]
M.Seth,T.Ziegler, M.Krykunov, J.Autschbach J.Chem.Phys. J. Chem. Phys. 128, 144105 (2008)
€
Evaluation of - X(1),Y(1)( )
€
Evaluation of - X(1),Y(1)( )
€
Introducing the unitary transformation U =1 1
1 -1
⎛
⎝ ⎜
⎞
⎠ ⎟
€
UA(0) B(0)
B(0)* A(0)*
⎛
⎝ ⎜
⎞
⎠ ⎟−ωI
(0) −I 0
0 I
⎛
⎝ ⎜
⎞
⎠ ⎟
⎛
⎝ ⎜ ⎜
⎞
⎠ ⎟ ⎟U
+UX I
(1)
YI(1)
⎛
⎝ ⎜
⎞
⎠ ⎟=U ωI
(1) −I 0
0 I
⎛
⎝ ⎜
⎞
⎠ ⎟−
A(1) B(1)
B(1)* A(1)*
⎛
⎝ ⎜
⎞
⎠ ⎟
⎛
⎝ ⎜ ⎜
⎞
⎠ ⎟ ⎟U
+UX I
(0)
YI(0)
⎛
⎝ ⎜
⎞
⎠ ⎟
€
ω I(0)I −Ω[ ]Z I
(1) = −ωI(0)S1/2(A(1) + B(1) )S−1/2FI
(0)
−ωI(0)S−1/2(A(1) − B(1) )S1/2FI
(0)
Here:Here:
€
Z I(1) = ωI
(0) S1/2(X I(1) +YI
(1) )
AffordsAffords
The Calculation of the B-termThe Calculation of the B-term
M.Seth,T.Ziegler, M.Krykunov, J.Autschbach J.Chem.Phys. J. Chem. Phys. 128, 144105 (2008)
The B term : practical calculations The B term : practical calculations
€
ω I(0)I −Ω[ ]Z I
(1) = −ωI(0)S1/2(A(1) + B(1) )S−1/2FI
(0)
−ωI(0)S−1/2(A(1) − B(1) )S1/2FI
(0)
€
An Expression for Kai,bj(1)
€
An Expression for Kai,bj(1)
€
We need φp(1). A well known expresson exists that is particularly simple because we have an
imaginary perturbation
€ €
€
φp(1) = Uqp
(1)φq(0) Uqp
(1) =H pq
(1)
εq(0) −ε p
(0)q≠ p
∑
€
φp(1) = Uqp
(1)φq(0) Uqp
(1) =H pq
(1)
εq(0) −ε p
(0)q≠ p
∑
€
Where H(1) is the Hamiltonian describing the perurbation
Thus
€
Kai,bj(1) = U pa
(1)*K pi,bj(0)
p≠a
∑ + U pi(1)*Kap,bj
(0) + U pb(1)*Kai,pj
(0)
p≠b
∑p≠i
∑ + U pb(1)*Kap,bp
(0)
p≠ j
∑
€
Kai,bj(1) = U pa
(1)*K pi,bj(0)
p≠a
∑ + U pi(1)*Kap,bj
(0) + U pb(1)*Kai,pj
(0)
p≠b
∑p≠i
∑ + U pb(1)*Kap,bp
(0)
p≠ j
∑
The Calculation of the B-termThe Calculation of the B-term
Seth+Ziegler JCP,2008,in pressSeth+Ziegler JCP,2008,in pressM.Seth,T.Ziegler, M.Krykunov, J.Autschbach J.Chem.Phys. J. Chem. Phys. 128, 144105 (2008)
The B term : Direct method The B term : Direct method
We must solve We must solve
€
AX = b€
ω I(0)I −Ω[ ]Z I
(1) = −ωI(0)S1/2(A(1) + B(1) )S−1/2FI
(0)
−ωI(0)S−1/2(A(1) − B(1) )S1/2FI
(0)
€
Our equation has the form
€
Our equation has the form
€
With A a known matrix, b a known vector and X the unknown vector to be determined. This
equation can be solved easily if we have A−1. There are two problems however
€
With A a known matrix, b a known vector and X the unknown vector to be determined. This
equation can be solved easily if we have A−1. There are two problems however
€
(a) The matrix A =ωI(0)I −Ω. This matrix has no inverse because ωI
(0)I is an eigenvalue of Ω
€
(b) The matrix A is extremely large and we don' t want to try and invert it directly.
€
To avoid this problem we :
€
To avoid this problem we :
€
(i) Solve the equations iteratively by expanding the solution in a Krylov
subspace(the space b,Ab, A2b,...Aib in the ith iteration)
€
(ii) Project out from the Krylov supspaces any contribution from FI(0)
The Calculation of the B-term by Direct MethodThe Calculation of the B-term by Direct Method
Seth+Ziegler JCP,2008Seth+Ziegler JCP,2008
The B term : Direct Method The B term : Direct Method
We must solve We must solve
€
Ax = b
€
(i) Can be used in conjunction with an unperturbed
TDDFT calculation that yields only a few solutions F(0).
€
(ii)Degree of convergence is known
ProsPros
ConsCons
€
(i) The iterative procedure is often slowly convergent.
We are attempting to improve convergence by adding
the unperturbed TDDFT solutions FJ(0), J ≠ I to Krylov subspace
€
BAJ = −2i
3εαβγ
αβγ
∑ M β S−1/2
ωJ(0)
(Z J(1)α )M λ (XJ
(0) +YJ(0) )
€
ω I(0)I −Ω[ ]Z I
(1) = −ωI(0)S1/2(A(1) + B(1) )S−1/2FI
(0)
−ωI(0)S−1/2(A(1) − B(1) )S1/2FI
(0)
The Calculation of the B-term by Direct MethodThe Calculation of the B-term by Direct Method
Seth+Ziegler JCP,2008,in pressSeth+Ziegler JCP,2008,in pressM.Seth,T.Ziegler, M.Krykunov, J.Autschbach J.Chem.Phys. J. Chem. Phys. 128, 144105 (2008)
The B term : Sum Over State The B term : Sum Over State
€
ω I(0)I −Ω[ ]Z I
(1) = −ωI(0)S1/2(A(1) + B(1) )S−1/2FI
(0)
−ωI(0)S−1/2(A(1) − B(1) )S1/2FI
(0)
€
Z (1) by Sum - Over - State
€
Z (1) by Sum - Over - State
€
Z I(1) = CJIFJ
(0)
J≠I
∑
€
Z I(1) = CJIFJ
(0)
J≠I
∑
€
Substitute into first order equation and multiply by FJ(0) from left affords
€
FJ(0)+ ωI
(0)I −Ω[ ]( (CJIFJ(0)
J≠I
∑ ) = −ωI(0)FJ
(0)+S1/2 (A(1) + B(1) )S−1/2FI(0)
−ωI(0)FJ
(0)+S−1/2(A(1) − B(1) )S1/2FI(0)
OrOr
€
CJI =−ωI
(0)(FJ(0)+S1/2(A(1) + B(1) )S−1/2FI
(0) + FJ(0)+S−1/2(A(1) − B(1) )S1/2FI
(0)
ωI(0) −ωJ
(0)
Writing Z(1) in terms of the complete set F(0) affordsWriting Z(1) in terms of the complete set F(0) affords
The Calculation of the B-term by Sum-over-State MethodThe Calculation of the B-term by Sum-over-State Method
Seth+Ziegler JCP,2008,134108Seth+Ziegler JCP,2008,134108M.Seth,T.Ziegler, M.Krykunov, J.Autschbach J.Chem.
Phys. J. Chem. Phys. 128, 144105 (2008)
The B term : Sum Over State The B term : Sum Over State
€
Z (1) by Sum - Over - State : Z I(1) = CJI
J≠I
∑ FJ(0)
€
CJI =−ωI
(0)(FJ(0)+S1/2(A(1) + B(1) )S−1/2FI
(0)
ωI(0) −ωJ
(0)+
+FJ(0)+S−1/2(A(1) − B(1) )S1/2FI
(0)
ωI(0) −ωJ
(0)
€
BAJ = −2i
3εαβγ
αβγ
∑ M β S−1/2
ωJ(0)
(Z J(1)α )M λ (XJ
(0) +YJ(0) )
€
BAJ = −2i
3εαβγ
αβγ
∑ M β S−1/2
ωJ(0)
(Z J(1)α )M λ (XJ
(0) +YJ(0) )
ProsPros
€
Interpretation easy in terms of contributions
from different excited statesConsCons
€
May need to calculate many FJ(0) in unperturbed
TDDFT and convergence of summation is unknown
The Calculation of the B-term by Sum-over-State MethodThe Calculation of the B-term by Sum-over-State Method
Seth+Ziegler JCP,2008,134108Seth+Ziegler JCP,2008,134108
Other B-term implementations Other B-term implementations
7S.Coriani, P.Jørgensen, T.Helgaker J.Chem.Phys. 113,3561,2000
HF+CI
CCSD(T)
E.Dalgaard Phys.Rev. A 42 42 1982
J.Olsen; P. Jørgensen J.Chem.Phys. 82 3235 (1985)
W.A.Parkinson; J.Oddershede J.Chem.Phys. 94,7251 (1991)
W.A.Parkinson; J.Oddershede) Int.J.Quantum Chem. 64,599 (1997)
T.Kjœrgaard, B.Jansik, P.Jørgensen,S.Coriani, J.Michl, J.Phys.Chem. A 111,11278 (2007))
DFT
H.Solheim; L.Frediani; K.Rudd; S.Coriani Theor.Chem.Acc 119,231,2007
DFT-SOS
M.Krykunov,M.Seth,T.Ziegler,J.Autschbach J.Chem.Phys. 2007,127,244107
M.Seth,T.Ziegler,J.Autschbach J.Chem.Theory.Comp.3,434,2007
J.Michl J.Am.Chem.Soc. 100, 6801, 1978
M.Seth,T.Ziegler, M.Krykunov, J.Autschbach J.Chem.Phys. J. Chem. Phys. 128, 144105 (2008)
Convergence of SOS-method for Ethylene Convergence of SOS-method for Ethylene
Comparison of Sum-over-State and Direct Method for B-termsComparison of Sum-over-State and Direct Method for B-terms
€
π → π *
€
π → 3s
€
π → 3s
€
π → π *
Seth+Ziegler JCP,2008Seth+Ziegler JCP,2008
Comparison of Direct Method for B-terms with ExperimentComparison of Direct Method for B-terms with Experiment
Exp: J.W.Waluk, J.Michl Inorg.Chem. 21,556,1982) Exp: H.-P.Klein, R.T. Oakley, J.Michl Inorg.Chem. 25,3194 (1986)
S4N3+ S4N2
Comparison of Direct Method for B-terms with ExperimentComparison of Direct Method for B-terms with Experiment
Exp: H.-P.Klein, R.T. Oakley, J.Michl Inorg.Chem. 25,3194 (1986)
Exp: H.-P.Klein, R.T. Oakley, J.Michl Inorg.Chem. 25,3194 (1986) Seth+Ziegler JCP,2008Seth+Ziegler JCP,2008
Comparison of Direct Method for B-terms with Experiment and other MethodsComparison of Direct Method for B-terms with Experiment and other Methods
Exp: H.-P.Klein, R.T. Oakley, J.Michl Inorg.Chem. 25,3194 (1986)
T.Kjœrgaard, B.Jansik, P.Jørgensen,S.Coriani, J.Michl, J.Phys.Chem. A 111,11278 (2007))
TD-DFT calculations of B-term. TD-DFT calculations of B-term.
Furan
Thiophene
Selenophen
Tellurophen
S
Se
Te
OW. Hieringer, S. J. A. van Gisbergen, and E. J. BaerendsJ. Phys. Chem. A 2002, 106, 10380
X
1a2
1b1
2b1
11A1 --> 21A1
11A1 --> 11B2
X
X
X 1b2 11A1 --> 11B1
Seth+Ziegler JCP,2008,134108Seth+Ziegler JCP,2008,134108
TD-DFT calculations of B-term. Sum-over-state formulationTD-DFT calculations of B-term. Sum-over-state formulation
Norden, B.; Hansson, R.; Pedersen, P. B.; Thulstrup, E. W. Chem.Phys. 1978, 33, 355.
TD-DFT calculations of B-term. Sum-over-state formulationTD-DFT calculations of B-term. Sum-over-state formulation
Norden, B.; Hansson, R.; Pedersen, P. B.; Thulstrup, E. W. Chem.Phys. 1978, 33, 355.
TD-DFT calculations of B-term. Sum-over-state formulationTD-DFT calculations of B-term. Sum-over-state formulation
Furan
O
6.0 6.2
0.20
-5.05 0.0 3.37
.13
€
1a2 → 3b1
€
2b1 → 3b1
Seth+Ziegler JCP,2008,134108Seth+Ziegler JCP,2008,134108
TD-DFT calculations of B-term. Sum-over-state formulationTD-DFT calculations of B-term. Sum-over-state formulation
Thiophene
S
5.5 5.7
450 6-477
.04
5.9
.13
€
1a2 → 3b1
€
2b1 → 3b1
Seth+Ziegler JCP,2008,134108Seth+Ziegler JCP,2008,134108
TD-DFT calculations of B-term. Sum-over-state formulationTD-DFT calculations of B-term. Sum-over-state formulation
Selonophene
Se
5.1 5.3
0.22
59.1 -3 -101
.07
5.5
€
1a2 → 3b1
€
2b1 → 3b1
Seth+Ziegler JCP,2008,134108Seth+Ziegler JCP,2008,134108
TD-DFT calculations of B-term. Sum-over-state formulationTD-DFT calculations of B-term. Sum-over-state formulation
TellurophenX
1a2
1b1
2b1
11A1 --> 21A1
11A1 --> 11B2
X
X
X 1b2 11A1 --> 11B1
Te
4.4 4.8
0.64
-5.1 -28.012.8
5.24.4 4.8
0.64
-5.1 -28.012.8
5.2
Seth+Ziegler JCP,2008,134108Seth+Ziegler JCP,2008,134108
A-term of MCDA-term of MCD
€
ΔAJ'
hω=
γo
1
3γ
∑ (NA − N Jλ )
NJλ∑ A ˆ M γ
− Jλ2
− A ˆ M γ+ Jλ
2 ⎛ ⎝ ⎜ ⎞
⎠ ⎟⋅
∂
∂Bγ
f (ω −ωJλ )( )0B
+γo
1
3γ
∑ (NA − N Jλ )
N
∂
∂BγJλ
∑ A ˆ M γ− Jλ
2− A ˆ M γ
+ Jλ2 ⎛
⎝ ⎜ ⎞
⎠ ⎟o
⋅ f (ω −ωJλ )( )B
+γo
1
3γ
∑ ∂
∂Bγ
(NA − N Jλ )
N
⎛
⎝ ⎜
⎞
⎠ ⎟0
Jλ∑ A ˆ M γ
− Jλ2
− A ˆ M γ+ Jλ
2 ⎛ ⎝ ⎜ ⎞
⎠ ⎟⋅ f (ω −ωJλ )( )B
€
ΔAJ'
hω=
γo
1
3γ
∑ (NA − N Jλ )
NJλ∑ A ˆ M γ
− Jλ2
− A ˆ M γ+ Jλ
2 ⎛ ⎝ ⎜ ⎞
⎠ ⎟⋅
∂
∂Bγ
f (ω −ωJλ )( )0B
+γo
1
3γ
∑ (NA − N Jλ )
N
∂
∂BγJλ
∑ A ˆ M γ− Jλ
2− A ˆ M γ
+ Jλ2 ⎛
⎝ ⎜ ⎞
⎠ ⎟o
⋅ f (ω −ωJλ )( )B
+γo
1
3γ
∑ ∂
∂Bγ
(NA − N Jλ )
N
⎛
⎝ ⎜
⎞
⎠ ⎟0
Jλ∑ A ˆ M γ
− Jλ2
− A ˆ M γ+ Jλ
2 ⎛ ⎝ ⎜ ⎞
⎠ ⎟⋅ f (ω −ωJλ )( )B
€
ΔAJ'
ω= −γoA J
∂f (ω −ωJλ )
∂ω+γ0B J f (ω −ωJλ )B +γoC J f (ω −ωJλ )B
€
ΔAJ'
ω= −γoA J
∂f (ω −ωJλ )
∂ω+γ0B J f (ω −ωJλ )B +γoC J f (ω −ωJλ )B
Origin of A-term Origin of A-term
M.Seth,T.Ziegler,J.Chem.Phys. 2004,120,10943
M.Seth,T.Ziegler, M.Krykunov, J.Autschbach J.Chem.Phys. J. Chem. Phys. 128, 234102 (2008)
The A-term of Magnetic Circular Dichroism (MCD) SpectroscopyThe A-term of Magnetic Circular Dichroism (MCD) Spectroscopy
The A term The A term
€
γo -A J
∂f (ω −ωJ )
∂ω
⎡ ⎣ ⎢
⎤ ⎦ ⎥J
∑ B
= γo
1
3γ
∑ (NA − N Jλ )
NJλ∑ A ˆ M γ
− Jλ2
− A ˆ M γ+ Jλ
2 ⎛ ⎝ ⎜ ⎞
⎠ ⎟⋅
∂
∂Bγ
f (ω −ωJλ )( )0B
= γo
1
3γ
∑ (NA − N Jλ )
NJλ∑ A ˆ M γ
− Jλ2
− A ˆ M γ+ Jλ
2 ⎛ ⎝ ⎜ ⎞
⎠ ⎟⋅
∂ωJλ
∂Bγ
⎛
⎝ ⎜ ⎜
⎞
⎠ ⎟ ⎟0
∂f (ω −ωJ )
∂ωB
ThusThus
€
A J = −λ
∑ 1
3γ
∑ (NA − N Jλ )
NA ˆ M γ
− Jλ2
− A ˆ M γ+ Jλ
2 ⎛ ⎝ ⎜ ⎞
⎠ ⎟0
⋅∂ωJλ
∂Bγ
⎛
⎝ ⎜ ⎜
⎞
⎠ ⎟ ⎟
M.Seth,T.Ziegler,J.Chem.Phys. 2004,120,10943
M.Seth,T.Ziegler, M.Krykunov, J.Autschbach J.Chem.Phys. J. Chem. Phys. 128, 234102 (2008)
The A-term of Magnetic Circular Dichroism (MCD) SpectroscopyThe A-term of Magnetic Circular Dichroism (MCD) Spectroscopy
The A term The A term
€
A J = −λ
∑ 1
3γ
∑ (NA − N Jλ )
NA ˆ M γ
− Jλ2
− A ˆ M γ+ Jλ
2 ⎛ ⎝ ⎜ ⎞
⎠ ⎟0
⋅∂ωJλ
∂Bγ
⎛
⎝ ⎜ ⎜
⎞
⎠ ⎟ ⎟
We haveWe have
ThusThus
M.Seth,T.Ziegler, M.Krykunov, J.Autschbach J.Chem.Phys. J. Chem. Phys. 128, 234102 (2008)
HereHere
€
ωλ2 = FJλ
T ΩFJλ
The A term The A term
€
A−'
hω−
A+'
hω=
ΔA'
hω= γβB -A J
∂ρA .J (hω)
∂(hω)+ (B J +
C J
kT)ρA .J (hω)
⎡
⎣ ⎢ ⎤
⎦ ⎥J∑
€
A−'
hω−
A+'
hω=
ΔA'
hω= γβB -A J
∂ρA .J (hω)
∂(hω)+ (B J +
C J
kT)ρA .J (hω)
⎡
⎣ ⎢ ⎤
⎦ ⎥J∑
-A+
A-ΔA
B=0
RCP LCP
1S
1P
B=0
-A+
A-
ΔA-
B>0
RCP LCP
O
-1
1
0
B>0
€
A ˆ M Jλ =r
∑ M rS−1/ 2FLλ(0)v
e r
€
A ˆ M Jλ =r
∑ M rS−1/ 2FLλ(0)v
e r
The A-term of Magnetic Circular Dichroism (MCD) SpectroscopyThe A-term of Magnetic Circular Dichroism (MCD) Spectroscopy
€
ˆ L = ˆ l ij=1
n
∑ = −ir r i
j=1
n
∑ ×r
∇ i
Other A-term implementations Other A-term implementations
7S.Coriani, P.Jørgensen, T.Helgaker J.Chem.Phys. 113,3561,2000
HF+CI
CCSD(T)
Y.Honda, M.Hada, M.Ehara, H.Nakatsuiji,J.Downing,J.Michl , Chem.Phys.Lett 355,219, , 2002
T.Kjœrgaard, B.Jansik, P.Jørgensen,S.Coriani, J.Michl, J.Phys.Chem. A 111,11278 (2007))
DFT
H.Solheim; ; K.Rudd; S.Coriani ,P.Norman J.Chem.Phys. 128,094193,2008
J.Michl J.Am.Chem.Soc. 100, 6801, 1978
Y.Honda, M.Hada, M.Ehara, H.Nakatsuiji,J.Michl , J.Chem.Phys. 123,164113 (2005)
M.Krykunov,M.Seth,T.Ziegler,J.Autschbach J.Chem.Phys. 2007,127,244107
M.Seth,T.Ziegler, E.J.Baerends J.Chem.Phys. 2004,120,10943
M.Seth,T.Ziegler, J.Chem.Phys. 2007,127,134108
M.Seth,T.Ziegler, M.Krykunov, J.Autschbach J.Chem.Phys. J. Chem. Phys. 128, 234102 (2008)
Applications:A/D
Se42+ Te4
2+
Fe(CN)64-
Ni(CN)42- C6Cl6
C6H3Br3
Oh
D4hD4h
D6h
D3h
Exp: 0.72Calc: 0.63
Exp: 0.60Calc: 0.55Exp: 0.40 Calc: 0.48
Exp:-0.66Calc:-0.72Exp:-0.50Calc:-0.80
M.Seth,T.Ziegler,J.Chem.Phys. 2004,120,10943
€
AD
∝∂ω∂B
Positive A-term
Negative A-termNegative
B-termPositive B-term
Different MCD-terms
Absorption band
3t2
2e
t1
2t2
Metal
Ligand
3t2
2e
t1
2t2
Metal
Ligand
M.Seth,T.Ziegler, M.Krykunov, J.Autschbach J.Chem.Phys. J. Chem. Phys. 128, 234102 (2008)
MCD-terms for Oxyanions MCD-terms for Oxyanions
M.Seth,T.Ziegler, M.Krykunov, J.Autschbach J.Chem.Phys. J. Chem. Phys. 128, 234102 (2008)
Exp.Theor
MCD-terms for Thioanions MCD-terms for Thioanions
M.Krykunov,M.Seth,T.Ziegler,J.Autschbach J.Chem.Phys. Submitted
N
MN N
N
Alejandro Gonzales, Mike Seth, Tom Ziegler Inorg.Chem.
Inorg. Chem. 2007,46, 9111-9125. Alejandro Gonzales, Mike Seth, Tom Ziegler Inorg.Chem.
Inorg. Chem. 2007,46, 9111-9125.
MCD spectra of Porphyrins containing Mg,Ni and ZnMCD spectra of Porphyrins containing Mg,Ni and Zn
21Eu 31Eu
5 10-2
2e1.g
2a2.u
1a2.u
1a1.u
1b2.u1e1.g
ZnP
1b1.g
Orbital level diagram for ZnPOrbital level diagram for ZnP
2a2u
1a1u
1b2u
E.J. Baerends , G. Ricciardi , A. Rosa , S.J.A van GisbergenJ.Phys.Chem. A2001,105,3311
E.J. Baerends , G. Ricciardi , A. Rosa , S.J.A van GisbergenCoord.Chem.Rev. 2002,230,5
2eg2
2eg1
21Eu 31Eu
5 10-2
Exc. Energ. (eV) Complex Symmetry
exp. calc. Composition % h
f Assig n.
2a 2u -> 2e g 52.10 1E u
2.03 c, 2.21 d,
2.23 e , 2.18 f
2.28 1a 1u -> 2e g 46.63
0.001 Q
1b 2u -> 2e g 68.44
1a 1u -> 2e 1g 17.54 2E u 2.95 c, 3.09 d,
3.18 e
, 3.13 f 3.25
2a 2u -> 2e g 10.05 0.496
1b 2u -> 2e g 29.88 2a 2u -> 2e g 29.31 1a 1u -> 2e g 27.13
ZnP
3E u
3.32
1a 2u -> 2e g 10.30
0.943
Bg
Experimental Spectrum for ZnPExperimental Spectrum for ZnP
E.J. Baerends , G. Ricciardi , A. Rosa , S.J.A van GisbergenCoord.Chem.Rev. 2002,230,5
E.J. Baerends , G. Ricciardi , A. Rosa , S.J.A van GisbergenCoord.Chem.Rev. 2002,230,5
1Eu C1Φ(2a2u → 2eg)+C2Φ(1a1u --> 2eg)Gouterman State
2Eu
3Eu
C2Φ(2a2u → 2eg)-C1Φ(1a1u --> 2eg)Conjugated Gouterman State
Φ(1b2u → 2eg)
1A1g Ground State
1Eu C1Φ(2a2u → 2eg)+C2Φ(1a1u --> 2eg)Gouterman State
2Eu
3Eu
C2Φ(2a2u → 2eg)-C1Φ(1a1u --> 2eg)Conjugated Gouterman State
Φ(1b2u → 2eg)
1A1g Ground State
2e1.g
2a2.u
1a2.u
1a1.u
1b2.u1e1.g
ZnP
1b1.g
21Eu 31Eu
5 10-2
21Eu 31Eu
5 10-2
Experimental Spectrum for ZnPExperimental Spectrum for ZnP
L.Edwards,D.H.Dolphin,M.Goutermn J.Mol.Spectrosc 35(1970)90
E.J. Baerends , G. Ricciardi , A. Rosa , S.J.A van GisbergenCoord.Chem.Rev. 2002,230,5
1Eu C1Φ(2a2u → 2eg)+C2Φ(1a1u --> 2eg)Gouterman State
2Eu
3Eu
C2Φ(2a2u → 2eg)+C1Φ(1a1u --> 2eg)Conjugated Gouterman State
Φ(1b2u → 2eg)
1A1g Ground State
1Eu C1Φ(2a2u → 2eg)+C2Φ(1a1u --> 2eg)Gouterman State
2Eu
3Eu
C2Φ(2a2u → 2eg)+C1Φ(1a1u --> 2eg)Conjugated Gouterman State
Φ(1b2u → 2eg)
1A1g Ground State
€
D(1Eu ) = C1 2a2u y 2egy +C2 1a1u y 2egx[ ]2
1
22.92 −
1
23.25
⎡ ⎣ ⎢
⎤ ⎦ ⎥
2
= 2.27x10−2
€
D(3Eu ) = C1 2a2u y 2egy +C2 1a1u y 2egx[ ]2
1
22.92 +
1
23.25
⎡ ⎣ ⎢
⎤ ⎦ ⎥
2
= 9.51
Simulated Spectrum for ZnP with A-term onlySimulated Spectrum for ZnP with A-term only
ZnP Exp
A-only
Comp l ex Sy m m e try h
A
h
A/D
1E u 0.05 5.49
2E u - 3.37 - 1.62
ZnP
3E u - 0.57 - 0.15
1Eu
2Eu+3Eu
Q
Q
S
Alejandro Gonzales, Mike Seth, Tom Ziegler Inorg.Chem. Inorg. Chem. 2007,46, 9111-9125. Alejandro Gonzales, Mike Seth, Tom Ziegler Inorg.Chem. Inorg. Chem. 2007,46, 9111-9125.
Influence of ring distortion on MCD spectrum of ZnPInfluence of ring distortion on MCD spectrum of ZnP
€
B(nB1) = Im−2
3
nB1ˆ L z nB2 A1
ˆ M x nB1 nB2ˆ M y A1
ΔWn
⎧ ⎨ ⎪
⎩ ⎪
⎫ ⎬ ⎪
⎭ ⎪
€
B(nB2 ) = Im2
3
nB1ˆ L z nB2 A1
ˆ M x nB1 nB2ˆ M y A1
ΔWn
⎧ ⎨ ⎪
⎩ ⎪
⎫ ⎬ ⎪
⎭ ⎪
€
B (nB1)
€
B (nB2)
€
B (nB1) + B (nB2)
€
A (nEu)
N
N
N
N
M
ω
nB1
nB2
C2vD4h
nEu
N
N
N
N
M
Influence of ring distortion on MCD spectrum of ZnPInfluence of ring distortion on MCD spectrum of ZnP
2.00 2.50 3.00 3.50E(eV)
ZnPx10
Normalized Intensity-0.5
0.50.0
Dist C2V
2.00 2.50 3.00 3.50E(eV)
ZnPx10
Normalized Intensity-0.5
0.50.0
D4h
€
B(nB1) = Im−2
3
nB1ˆ L z nB2 A1
ˆ M x nB1 nB2ˆ M y A1
ΔWn
⎧ ⎨ ⎪
⎩ ⎪
⎫ ⎬ ⎪
⎭ ⎪
€
B(nB2 ) = Im2
3
nB1ˆ L z nB2 A1
ˆ M x nB1 nB2ˆ M y A1
ΔWn
⎧ ⎨ ⎪
⎩ ⎪
⎫ ⎬ ⎪
⎭ ⎪
N
N
N
N
M
ω
nB1
nB2
C2vD4h
nEu
N
N
N
N
M
Simulated Spectrum for ZnP with B-term onlySimulated Spectrum for ZnP with B-term only
Exp.
€
B(nEu ) = Im−4
3 p≠n
∑nEux
ˆ L z pEuy A1gˆ M x nEux pEuy
ˆ M y A1g
W ( pE1uy )− W (nE1uy )
⎧ ⎨ ⎪
⎩ ⎪
⎫ ⎬ ⎪
⎭ ⎪
1Eu 2Eu3Eu
B-terms
Simulated Spectrum forZnP with A+B-term onlySimulated Spectrum forZnP with A+B-term only
E (eV) E (eV)
x 100
ZnP
-0.50
0.00
0.50
1.00
Normalized Intensity
2.00 2.50 3.00 3.50
Exp.
€
B (3Eu ) =
Im−4
3 p≠n
∑3Eux
ˆ L z 2Euy A1gˆ M x 3Eux 2Euy
ˆ M y A1g
W (2E1uy ) −W (3E1uy )
⎧ ⎨ ⎪
⎩ ⎪
⎫ ⎬ ⎪
⎭ ⎪
€
B (2Eu ) =
Im−4
3 p≠n
∑2Eux
ˆ L z 3Euy A1gˆ M x 2Eux 3Euy
ˆ M y A1g
W (3E1uy ) −W (2E1uy )
⎧ ⎨ ⎪
⎩ ⎪
⎫ ⎬ ⎪
⎭ ⎪
€
B (3Eu ) =
Im−4
3 p≠n
∑2Eux
ˆ L z 3Euy A1gˆ M x 3Eux 2Euy
ˆ M y A1g
W (2E1uy ) −W (3E1uy )
⎧ ⎨ ⎪
⎩ ⎪
⎫ ⎬ ⎪
⎭ ⎪
= −B (2Eu )
Alejandro Gonzales, Mike Seth, Tom Ziegler Inorg.Chem.
Inorg. Chem. 2007,46, 9111-9125. Alejandro Gonzales, Mike Seth, Tom Ziegler Inorg.Chem.
Inorg. Chem. 2007,46, 9111-9125.
Simulated Spectrum for MgP and NiP with A+B-termSimulated Spectrum for MgP and NiP with A+B-term
2eg 2eg 2eg
2a2u2a2u2a2u
1a1u
1a2u 1a2u 1a2u
1a1u1a1u
1b2u1b2u1b2u
dxy
1eg 1eg
1egdxz, dyz
1eu
dxz, dyz
dx2-y2
dz2
MgP NiP ZnP-7.00
-9.50
-12.00
E(eV)
1b1g
2eg 2eg 2eg
2a2u2a2u2a2u
1a1u
1a2u 1a2u 1a2u
1a1u1a1u
1b2u1b2u1b2u
dxy
1eg 1eg
1egdxz, dyz
1eu
dxz, dyz
dx2-y2
dz2
MgP NiP ZnP-7.00
-9.50
-12.00
E(eV)
1b1g
2.0 2.5 3.0 3.5
E(eV)
(a) MgP
0.0
0.5
0.5
x100
2.0 2.5 3.0 3.5
E(eV)
(a) MgP
0.0
0.5
0.5
x100
2.0 2.5 3.0 3.5
E(eV)
0.0
0.5
0.5
(b) NiP
x100
2.0 2.5 3.0 3.5
E(eV)
0.0
0.5
0.5
(b) NiP
x100
1Eu
2Eu3Eu
Substituted Porphyrins Substituted Porphyrins
N
M
m
β
N N
N
N
MN N
N
MTPP
N
MN N
N
MOEPtetraphenylporphyrin octaethylporphyrin
Alejandro Gonzales, Mike Seth, Tom Ziegler Inorg.Chem.
Inorg. Chem. 2007,46, 9111-9125. Alejandro Gonzales, Mike Seth, Tom Ziegler Inorg.Chem.
Inorg. Chem. 2007,46, 9111-9125.
Excited States for Substituted Porphyrins Excited States for Substituted Porphyrins
2.00 2.50 3.00 3.50E(eV)
Normalized Intensity-0.5
0.5
0.0
NiTPP
N
NiN N
N
€
A (1Eu )
€
B (2Eu )
€
B (3Eu )
Alejandro Gonzales, Mike Seth, Tom Ziegler Inorg.Chem.
Inorg. Chem. 2007,46, 9111-9125. Alejandro Gonzales, Mike Seth, Tom Ziegler Inorg.Chem.
Inorg. Chem. 2007,46, 9111-9125.
Excited States for Substituted Porphyrins Excited States for Substituted Porphyrins
2.00 2.50 3.00 3.50E(eV)
Normalized Intensity-0.5
0.5
0.0
ZnTPP
x10
N
ZnN N
N
€
A (1Eu )
€
B (2Eu )
€
B (3Eu )
€
A (1Eu )
Alejandro Gonzales, Mike Seth, Tom Ziegler Inorg.Chem.
Inorg. Chem. 2007,46, 9111-9125. Alejandro Gonzales, Mike Seth, Tom Ziegler Inorg.Chem.
Inorg. Chem. 2007,46, 9111-9125.
Tetraazaporphyrins and PhthalocyaninesTetraazaporphyrins and Phthalocyanines
N
M
m
β
N N
N
Tetraazaporphyrins and PhthalocyaninesTetraazaporphyrins and Phthalocyanines
N
M
m
β
N N
N
N
M
N N
N N
NN N
MTAPtetraazaporphyrin
Tetraazaporphyrins and PhthalocyaninesTetraazaporphyrins and Phthalocyanines
N
M
m
β
N N
N
N
M
N N
N N
NN N
MTAPtetraazaporphyrin
N
M
N N
N N
NN N
MPcphthalocyanine
Alejandro Gonzales, Mike Seth, Tom Ziegler Inorg.Chem.
Inorg. Chem. 2008,46, 9111-9125. Alejandro Gonzales, Mike Seth, Tom Ziegler Inorg.Chem.
Inorg. Chem. 2008,46, 9111-9125.
Magnetic Circular Dichroism (MCD) SpectroscopyMagnetic Circular Dichroism (MCD) Spectroscopy
The C term The C term
€
A−'
hω−
A+'
hω=
ΔA'
hω= γβB -A J
∂ρA .J (hω)
∂(hω)+ (B J +
C J
kT)ρA .J (hω)
⎡
⎣ ⎢ ⎤
⎦ ⎥J∑
€
A−'
hω−
A+'
hω=
ΔA'
hω= γβB -A J
∂ρA .J (hω)
∂(hω)+ (B J +
C J
kT)ρA .J (hω)
⎡
⎣ ⎢ ⎤
⎦ ⎥J∑
1P
1S
M- M+
B=0
-A+
A-ΔA
B=0
1P+
1S
M- M+
B>0
1P-
ΔA-A+
A-
B>0
If
€
NP+− NP+
N tot
≈EP+
− EP+
3kT
€
EP+− EP+
<< kT
€
C = −i
3 AAα '
αa 'λ
∑ ˆ L Aα ⋅ Aα ˆ M Jλ × Jλ ˆ M Aα ' ⎛ ⎝ ⎜
⎞ ⎠ ⎟
€
C = −i
3 AAα '
αa 'λ
∑ ˆ L Aα ⋅ Aα ˆ M Jλ × Jλ ˆ M Aα ' ⎛ ⎝ ⎜
⎞ ⎠ ⎟
Electron configuration t1u6t2u
6t1u6t2g
5
Seth,Ziegler,Autschbach,Ziegler JCP, 2005,09412
Limitations of Traditional TD-DFTLimitations of Traditional TD-DFT
ix iy
What do we do with adegenerate ground statethat can not be representedby single Slater determinant ?
What do we do with adegenerate ground statethat can not be representedby single Slater determinant ?
Degenerate Ground StateDegenerate Ground State
a
ix iy
a
ix iy
What are thefundamentalequations ?
What are thefundamentalequations ?
How do we calculateexcitationenergies
How do we calculateexcitationenergies
TRICKS of the Trade: Calculating the Excitation Energies of Molecules with Degenerate Ground States using TD-DFTTRICKS of the Trade: Calculating the Excitation Energies of Molecules with Degenerate Ground States using TD-DFT
• Degenerate ground states are generally treated within DFT by fractional occupations of the degenerate orbital. This gives a ground state of indeterminent symmetry.
• Degenerate ground states are generally treated within DFT by fractional occupations of the degenerate orbital. This gives a ground state of indeterminent symmetry.
ChallengesChallenges
• A degenerate ground state can be made non-degenerate by breaking utilizing a lower symmetry point group. The amount of symmetry breaking in this case can be large and symmetry assignments complicated
• A degenerate ground state can be made non-degenerate by breaking utilizing a lower symmetry point group. The amount of symmetry breaking in this case can be large and symmetry assignments complicated
Transformed Reference with an Intermediate ConfigurationKohn Sham (TRICKS) TDDFT
Solution:Solution:
TRICKS of the Trade: Calculating the Excitation Energies of Molecules with Degenerate Ground States using TD-DFTTRICKS of the Trade: Calculating the Excitation Energies of Molecules with Degenerate Ground States using TD-DFT
Idea:Idea:Avoid problems with a degenerate ground state by taking an excited state that is nondegenerate as the (Transformed) Reference Intermediate Configuration.
Example 1:d1 transition metal complexes of Oh symmetry,d-d transition
Example 1:d1 transition metal complexes of Oh symmetry,d-d transition
Application of the TRIC methodApplication of the TRIC method
€
TiF63−
Results 1:d1 transition metal complexes of Oh symmetry,d-d transition.
Results 1:d1 transition metal complexes of Oh symmetry,d-d transition.
Application of the TRIC methodApplication of the TRIC method
€
TiF63−
Example 2:d1 transition metal complexes of Td symmetry,d-d transition
Example 2:d1 transition metal complexes of Td symmetry,d-d transition
Application of the TRIC methodApplication of the TRIC method
€
VCl4
Result 2:d1 transition metal complexes of Td symmetry,d-d transition
Result 2:d1 transition metal complexes of Td symmetry,d-d transition
Application of the TRIC methodApplication of the TRIC method
€
VCl4
Example 3:d1 transition metal complexes of Td symmetry,charge transfer
Example 3:d1 transition metal complexes of Td symmetry,charge transfer
Application of the TRIC methodApplication of the TRIC method
€
VCl4
Result 3:d1 transition metal complexes of Td symmetry,charge transfer
Result 3:d1 transition metal complexes of Td symmetry,charge transfer
Application of the TRIC methodApplication of the TRIC method
€
VCl4
Application: Fe(CN)63-Application: Fe(CN)63-
Electron configuration t1u6t2u
6t1u6t2g
5
Excitations are ligand-metal charge transfer. C term of a transition to a T1u state is positive andto a T2u state is negative.
Transition Exp. Calc.
1 1.21/0.61 0.86
2 -0.68 -0.86
3 0.56 0.86
Seth,Ziegler,Autschbach,Ziegler JCP, 2005,09412
More Applications
RuCl63- [Fe(CN)5SCN]3-
MnPc
Exp. Calc.
0.58 0.84
-0.60 -0.84
Exp Calc
7.5 7.3
6.9 7.3
-6.9 -7.3
6.3 7.3
-3.1 -7.3
2.2 7.3
Exp. Calc.
0.03 0.90
0.23 0.90
Seth,Ziegler,Autschbach,Ziegler JCP, 2005,09412
|A>
|J>
|K>
JA <A|LAJ|J>
<J|r|A>
€
ε(1)
hω
<K|LAJ|J>
KJ
|A>
|J>
€
ε(2)
hω
|K>
<J|r|A><A|r|K>|A>
|J>
€
ε(3)
hω
<J|r|A>
|K><K|LAJ|A> KJ
Spin-degenerate Ground State MCD via Spin-orbit Coupling
M.L.Kirk Curr.Op.Chem.Bio 2003,220
Application to Plastocyanin
85 §M.E. I. Solomon, R.K. Szilagyi, S. D. George and L. Basumallick, Chem. Rev, 104, 419, 2004.
Application to Plastocyanin
<K|LAJ|J>
KJ
|A>
|J>
€
ε(2)
hω
|K>
<J|r|A><A|r|K>
Application to Sulfite Oxidase Application to Sulfite Oxidase
87 §M.E. Helton, A. Pacheco, J. McMaster, J.H. Enemark and M. Kirk, J. Inorg. Biochem., 80, 227, 2000.
Application to Sulfite Oxidase
L1: -SCH3. L2: -OH. L3: -S(CH2)2S-.
|A>
|J>
<J|r|A>
|K><K|LAJ|A> KJ
TD-DFT/MCD
Dr. Mike SethDr.Jochen Autschbach
Alejandro Gonzalez Peralta
Dr. Mykhaylo Krykunov
Fan Wang
Hristina Zhekova
PRF
Mitsui
MOR and MCD`MOR and MCD`
TD-DFT formulation without damping TD-DFT formulation without damping
€
We solve the equation
€
We solve the equation
€
ˆ h ks (v r )+V ext (
v r , t) − i
∂
∂t
⎡ ⎣ ⎢
⎤ ⎦ ⎥φk (r)× exp[−iε kt] = 0
To obtain the solutionTo obtain the solution
€
φk' (
v r , t) = C j (t)φ j
j≠i
∑ (v r )× exp[−iε jt]
€
Δρ ( y)(ω,r r ) = [X(ω)ai +Y (ω)ai ]φaφi
a
vir
∑i
occ
∑
From which we obtain density change in frequency domainFrom which we obtain density change in frequency domain
With:With:
€
(X(ω)+Y (ω)) = 2S−1/2[ω2 −Ω]−1S−1/2V (ω)
MOR and MCDMOR and MCD
€
Vsos (ω) = −γhω2B J
WJ2 −(hω)2
J
∑
€
Vsos (ω) = −γhω2B J
WJ2 −(hω)2
J
∑The expressionThe expression
Allows us to calculate the MOR parameter V( ) from the MCDparameters BJ after summing over all statesAllows us to calculate the MOR parameter V( ) from the MCDparameters BJ after summing over all states
aM. Krykunov, A. Banerjee, T. Ziegler,J. Autschbach J. Chem. Phys. 2005, 122, 075105,
MOR and MCDMOR and MCD
€
V (ω) = −γhω 2B J
WJ2 − (hω)2
J
∑
€
V (ω) = −γhω 2B J
WJ2 − (hω)2
J
∑The expressionThe expression
Vres(
€
Vdamp(ω)
€
The expression for V(ω) diverges for hω = WJ
€
The expression for V(ω) diverges for hω = WJ
We need a TD-DFT formulation in which damping includedWe need a TD-DFT formulation in which damping included
MOR and MCD`MOR and MCD`
TD-DFT formulation with damping TD-DFT formulation with damping
€
We solve the equation
€
We solve the equation
€
ˆ h ks (v r )+V ext (
v r , t) − i
∂
∂t
⎡ ⎣ ⎢
⎤ ⎦ ⎥φk (r)× exp[−iε kt]exp[−Γt] = 0
To obtain finite lifetime solutionsTo obtain finite lifetime solutions
€
φk' (
v r , t) = C j (t)φ j
j≠i
∑ (v r )× exp[−iε jt]exp[−λ t]
€
Δρ ( y)(ω,r r ) = [X(ω)ai +Y (ω)ai ]φaφi
a
vir
∑i
occ
∑
From which we obtain density change in frequency domainFrom which we obtain density change in frequency domain
With:
€
(X(ω)+Y (ω)) = 2S−1/2[(ω + iγ )2 −Ω]S−1/2V (ω)L.Jensen; J.Autchbach; G.C.Schatz J.Chem.Phys.2005,122,224115
MOR and MCD`MOR and MCD`
TD-DFT formulation with damping TD-DFT formulation with damping
€
Vresdm (ω) =Vres
R,dm (ω)+ iVresI ,dm
HereHere
€
VresR,dm (ω) =Vsos
R,dm (ω) ≡J
∑ 2ω2 (ωJ2 −ω2 )B J
(ωJ2 −ω2 )2 + 4ω2γ 2
€
VresI ,dm (ω) =Vsos
I ,dm (ω) ≡J
∑ 4ω3γB J
(ωJ2 −ω2 )2 + 4ω2γ 2andand
M.Krykunov,M.Seth,T.Ziegler,J.Autschbach J.Chem.Phys. 2007,submitted
MOR and MCD`MOR and MCD`
TD-DFT formulation with damping TD-DFT formulation with damping
€
VresR,dm (ω) =Vsos
R,dm (ω) ≡ γ0
J
∑ 2ω2(ωJ2 −ω2 )B J
(ωJ2 −ω2 )2 + 4ω2γ 2
oror
€
VsosR,dm (ω) =Vsos
udm (ω) fd (ω)
€
VsosR,dm (ω) =Vsos
udm (ω) fd (ω)
€
fd (ω) =
2(ωJ2 −ω2 )2
(ωJ2 −ω2 )2 + 4ω2γ 2
HereHere
€
Vsosudm (ω)
€
VsosR,dm (ω)
M.Krykunov,M.Seth,T.Ziegler,J.Autschbach J.Chem.Phys. 2007,submitted
MOR and MCDMOR and MCD
TD-DFT formulation with damping TD-DFT formulation with damping
€
VresI ,dm (ω) =Vsos
I ,dm (ω) ≡J
∑ 4ω3γB J
(ωJ2 −ω2 )2 + 4ω2γ 2
€
VresI ,dm (ω) /ω = γ0 ωB J
J
∑ fJ,B (ω) = Δε MCD (ω)oror
€
fJ,B (ω) =4ω γ
(ωJ2 −ω2 )2 + 4ω2γ 2
€
fJ,B (ω)
M.Krykunov,M.Seth,T.Ziegler,J.Autschbach J.Chem.Phys. 2007,submitted
MOR and MCDMOR and MCD
M.Krykunov,M.Seth,T.Ziegler,J.Autschbach J.Chem.Phys. 2007,submitted
€
VresI ,dm (ω) /ω = γ0 ωB J
J
n
∑ fJ,B (ω) = Δε MCD (ω)
€
We can obtain B J (j =1,n) from a least square fit of
€
D =i=1
m
∑ VresI ,dm (ωi ) /ωi −γ0 ωiB J
J
n
∑ fJ,B (ωi ) ⎛
⎝ ⎜
⎞
⎠ ⎟
2
For m>n
MCD spectra of Porphyrins containing Mg,Ni and ZnMCD spectra of Porphyrins containing Mg,Ni and Zn
N
MN N
N
N
MN N
N
MTPP
tetraphenylporphyrin
MOEP
tetraphenylporphyrin
N
M
N N
N N
NN N
MTAP
N
M
N N
N N
NN N
tetraazaporphyrin MPcphthalocyanine
porphyrin
MP
N
M
m
β
N N
N
Example 2:Double ExcitationsExample 2:Double Excitations
Application of the TRIC methodApplication of the TRIC method
Seth,M., Ziegler,T. , J. Chem. Phys., 2005,123, 144105,
Seth,M. ; Ziegler,T. J. Chem. Phys. 2006, 124, 144105
Groundstate
Excited state
TRIC state
The B term : practical calculations The B term : practical calculations
€
where A, B C are defined by
€
where A, B C are defined by
€
Aaiσ ,bjτ =δστ δabδij
εbτ −ε jτ
nbτ − n jτ
− Kaiσ ,bjτ
€
Kaiσ , jbτ = dr dr 'ϕ aσ* (r)∫∫ ϕ iσ (r)
1
r − r'ϕ bτ (r' )ϕ jτ
* (r' )
+ dr dr 'ϕ aσ* (r)∫∫ fXC (r,r',ω)ϕ bτ (r' )ϕ jτ
* (r' )
€
Baiσ ,bjτ = Kaiσ , jbτ
€
Caiσ ,bjτ =δστ δabδij
1
nbτ − n jτ
The Calculation of the B-termThe Calculation of the B-term
Limitations of Traditional TD-DFTLimitations of Traditional TD-DFT
ix iy
What do we do with adegenerate ground statethat can not be representedby a single Slater determinant ?
What do we do with adegenerate ground statethat can not be representedby a single Slater determinant ?
Degenerate Ground StateDegenerate Ground State
a
ix iy
a
ix iy
What are thefundamentalequations ?
What are thefundamentalequations ?
How do we calculateexcitationenergies
How do we calculateexcitationenergies
Transformed Reference with an Intermediate ConfigurationKohn Sham (TRICKS) TDDFT
Solution:Solution:
TRICKS of the Trade: Calculating the Excitation Energies of Molecules with Degenerate Ground States using TD-DFTTRICKS of the Trade: Calculating the Excitation Energies of Molecules with Degenerate Ground States using TD-DFT
Idea:Idea:Avoid problems with a degenerate ground state by taking an excited state that is nondegenerate as the (Transformed) Reference Intermediate Configuration.
A. I. Krylov, Acc. Chem. Res. 2006, 39, 83-91
Example 2:d1 transition metal complexes of Td symmetry,d-d transition
Example 2:d1 transition metal complexes of Td symmetry,d-d transition
Application of the TRIC methodApplication of the TRIC method
€
VCl4
Result 2:d1 transition metal complexes of Td symmetry,d-d transition
Result 2:d1 transition metal complexes of Td symmetry,d-d transition
Application of the TRIC methodApplication of the TRIC method
€
VCl4
Example 3:d1 transition metal complexes of Td symmetry,charge transfer
Example 3:d1 transition metal complexes of Td symmetry,charge transfer
Application of the TRIC methodApplication of the TRIC method
€
VCl4
Result 3:d1 transition metal complexes of Td symmetry,charge transfer
Result 3:d1 transition metal complexes of Td symmetry,charge transfer
Application of the TRIC methodApplication of the TRIC method
€
VCl4
Conclusion• Method for calculating the MCD A term (and dipole strength D)
within TD-DFT is outlined. Procedure for calculating C/D more straightforward.
• Implemented into the Amsterdam Density Functional Theory (ADF) program
• Applications to a range of small molecules
• Further information can be found in M. Seth, T Ziegler, A Banerjee, J. Autschbach, S.J.A. van Gisbergen E. J. Baerends, J. Chem. Phys. 120,10942, 2004 and M. Seth, T. Ziegler, J. Autschbach, J. Chem. Phys. accepted for publication.
MOR and MCDMOR and MCD
Consider a planar polarized light traveling a distance l through a media of randomly oriented molecules along the direction ofa constant magnetic field with strength B.
Consider a planar polarized light traveling a distance l through a media of randomly oriented molecules along the direction ofa constant magnetic field with strength B.
€
€
α =V (ω)Bl
Here V( ) is called the Verdet constantHere V( ) is called the Verdet constant
BE E
α
l
For such a system the plane of polarization will rotate by an angle given byFor such a system the plane of polarization will rotate by an angle given by
€
Vsos (ω) ≡ −μ 0cN
3
hω2B J
WJ2 − hω2
J
∑
€
Vsos (ω) ≡ −μ 0cN
3
hω2B J
WJ2 − hω2
J
∑
aM. Krykunov, A. Banerjee, T. Ziegler,J. Autschbach J. Chem. Phys. 2005, 122, 075105,
A.Banerjee,J.Autschbach,T.Ziegler Int.J.Quant.Chem.2006,101,572
MOR and MCDMOR and MCD
€
€
Vsos (ω) ≡ −μ 0cN
3
hω2B J
ωJ2 −ω2
J
∑
€
Vsos (ω) ≡ −μ 0cN
3
hω2B J
ωJ2 −ω2
J
∑€
VRe s (ω)€
VRe s (ω) =ωμ ocN
12Im[
∂
∂Bx
{α yz (ω) −α zy(ω}]ω≠ωJ
+ωμ ocN
12Im[
∂
∂By
{α zx (ω) −α xz (ω}]ω≠ωJ
+ωμ ocN
12[Im
∂
∂Bz
{α xy(ω) −α yz (ω)}]ω≠ωJ
ωμ ocN
12Imε stu
∂
∂Bu
(α st (ω)) Bu =0( )
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VRe s (ω) =ωμ ocN
12Im[
∂
∂Bx
{α yz (ω) −α zy(ω}]ω≠ωJ
+ωμ ocN
12Im[
∂
∂By
{α zx (ω) −α xz (ω}]ω≠ωJ
+ωμ ocN
12[Im
∂
∂Bz
{α xy(ω) −α yz (ω)}]ω≠ωJ
ωμ ocN
12Imε stu
∂
∂Bu
(α st (ω)) Bu =0( )
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∂αst (ω)
∂Bu
⎡
⎣ ⎢
⎤
⎦ ⎥ω≠ωJ
=
−Im [∂
∂Bu
Δρ (t )(ω,r r )]ω≠ωJ∫ xsd
r r
€
∂αst (ω)
∂Bu
⎡
⎣ ⎢
⎤
⎦ ⎥ω≠ωJ
=
−Im [∂
∂Bu
Δρ (t )(ω,r r )]ω≠ωJ∫ xsd
r r
€
B J
€
∂ααβ (ω)
∂Bγ
⎡
⎣ ⎢
⎤
⎦ ⎥
ω=ωJ
=
−Im [∂
∂Bλ
Δρ (β )(ω,r r )]ω=ωJ∫ xα d
r r
€
∂ααβ (ω)
∂Bγ
⎡
⎣ ⎢
⎤
⎦ ⎥
ω=ωJ
=
−Im [∂
∂Bλ
Δρ (β )(ω,r r )]ω=ωJ∫ xα d
r r
€
B J =
−i
3ε rst
∂α st (ω)
∂Br
⎛
⎝ ⎜
⎞
⎠ ⎟
r,s ,t
∑ω=ωL
M. Krykunov, A. Banerjee, T. Ziegler,J. Autschbach J. Chem. Phys. 2005, 122, 075105,
MOR and MCDMOR and MCD
€
VresI ,dm (ω) /ω = γ0 ωB J
J
n
∑ fJ,B (ω) = Δε MCD (ω)
€
We can obtain B J (j =1,n) from a least square fit of
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D =i=1
m
∑ VresI ,dm (ωi ) /ωi −γ0 ωiB J
J
n
∑ fJ,B (ωi ) ⎛
⎝ ⎜
⎞
⎠ ⎟
2
For m>n
M.Krykunov,M.Seth,T.Ziegler,J.Autschbach J.Chem.Phys. 2007,127,244107
MOR and MCDMOR and MCD
€
Δε
Furan Thiophene
Selenophen Tellurophene
M.Krykunov,M.Seth,T.Ziegler,J.Autschbach J.Chem.Phys. 2007,127,244107