the physical methods in inorganic chemistry (fall term, 2004) department of chemistry national sun...
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The Physical Methods in Inorganic Chemistr
y
(Fall Term, 2004)Department of Chemistry
National Sun Yat-sen University
無機物理方法(核磁共振部分)
Chapter 7
Introduction to Solid State NMR
• 7.0 Summary of internal interactions in solid state NMR
• 7.1 Typical lineshapes for static samples• 7.2 Magic-angle-spinning (MAS)• 7.3 Cross polarization (CP) and CPMAS• 7.4 Homonuclear decoupling pulse sequence
s• 7.5 Multi-quantum MAS (MQMAS) of qua
drupole spins
Single Crystal or Polycrystalline (Powder) Samples
Spin 1 creates a tiny magnetic field at spin 2 and vise versa, introducing direct magnetic coupling between them.
The magnetic field produced by spin 1 at the position of spin 2 is
]2,1)2,1(3[ 111
42,1 312
0 mm rrB r
Which causes an energy of amount
])2,1)(2,1(3[ 21211
42,12 312
0 mmmmmE rrB r
This is the same energy that the spin 1 gains from the magnetic field produced by the spin 2.
||12
12
12ˆr
rr
12r̂
1ˆˆˆˆˆˆ ,12,12,12,12,12,12 zzyyxx rrrrrr
(unit vector)
r1,2
1
2
1|ˆ| 12 r
Expressing the energy in quantum mechanics, we have the direct dipolar interaction Hamiltonian as
]))((3[ ,,3
20
4,, jiji
rijiiijD IIIIIH jiji rrB
ij
ji
ij
ij
]))((3[ 212142,12212, 2,12,1312
212
0 IIrIrIBIHrD
[with ]
2,1, iIm iii which can be written in compact form
i
j
X
Y
Z
zjziyjyixjxiji
zjizjyjiyjxjixjj
zjiziyjiyixjixii
IIIIIIII
rIrIrII
rIrIrII
ji
ji
r
r
,,,,,,
,,,,,,,,,
,,,,,,,,,
,
,
]))((3[]))((3[ ,,,,3
20
4,, jijiDijjijirijiiijD IIIIIIIIIH jirjirjirjirBij
ji
ij
ij
i
j
X
Y
Zzjizjixjziyjizjixjzixjizjixjzi
zjiyjizjyiyjiyjiyjyixjiyjixjyi
zjixjizjxiyjixjiyjxixjixjixjxi
zjizjyjiyjxjixj
zjiziyjiyixjixijijjii
rrIIrrIIrrII
rrIIrrIIrrII
rrIIrrIIrrII
rIrIrI
rIrIrIrIrI
,,,,,,,,,,,,,,,,,,
,,,,,,,,,,,,,,,,,,
,,,,,,,,,,,,,,,,,,
,,,,,,,,,
,,,,,,,,,,,
)(
)()ˆ()ˆ(
zjziyjyixjxiji IIIIIIII ,,,,,,(
jijiD IDIH
zjzzijziyjzyijzixjzxijzi
zjyxijyiyjyyijyixjyxijyi
zjxzijxiyjxyijxixjxxijxiD
IDIIDIIDI
IDIIDIIDI
IDIIDIIDIH
,,,,,,,,,
,,,,,,,,,
,,,,,,,,,
)1ˆˆ3(ˆˆ3ˆˆ3
ˆˆ3)1ˆˆ3(ˆˆ3
ˆˆ3ˆˆ3)1ˆˆ3(
,,,,,,,,,,,,
,,,,,,,,,,,,
,,,,,,,,,,,,
zjizjiDijyjizjiDijxjizjiDij
zjiyjiDijyjiyjiDijxjiyjiDij
zjixjiDijyjixjiDijxjixjiDij
ij
rrrrrr
rrrrrr
rrrrrr
D
jijiijD IDIH ,
)1ˆˆ3( ,,,,, xjixjiDijxxij rrD yjixjiDijxyij rrD ,,,,, ˆˆ3
)1ˆˆ3( ,,,,, yjiyjiDijyyij rrD
zjixjiDijxzij rrD ,,,,, ˆˆ3
xjiyjiDijyxij rrD ,,,,, ˆˆ3zjiyjiDijyzij rrD ,,,,, ˆˆ3
xjizjiDijzxij rrD ,,,,, ˆˆ3yjizjiDijzyij rrD ,,,,, ˆˆ3 )1ˆˆ3( ,,,,, zjizjiDijzzij rrD
It is symmetric It is traceless (see the reason?)
1ˆˆˆˆˆˆ ,,,,,, zijzijyijyijxijxij rrrrrr
where D is called dipolar coupling tensor.
Principal-Axis System (PAS)
0
)2( ,2,1,2,1,2,112,
,2,1,2,1,2,112,
zzyyxx
zzyyxxD
zzzzyyyyxxxxD
DDD
IIIIII
IIDIIDIIDH
)1ˆˆ3(ˆˆ3ˆˆ3
ˆˆ3)1ˆˆ3(ˆˆ3
ˆˆ3ˆˆ3)1ˆˆ3(
,,,,,,,,,,,,
,,,,,,,,,,,,
,,,,,,,,,,,,
zjizjiDijyjizjiDijxjizjiDij
zjiyjiDijyjiyjiDijxjiyjiDij
zjixjiDijyjixjiDijxjixjiDij
ij
rrrrrr
rrrrrr
rrrrrr
D
In the principal-axis system (PAS), only the diagonal elements of D are non-zero and
i
j
Dij
Dij
Dij
ijD
200
00
00
Spherical Coordinates
cos
sinsin
cossin
rz
ry
rx
(x,y,z)
r
HD in Spherical coordinates
)}()(2sin
)(2sin)]()[1cos3{(
,,2
,,2
4
sin3,,,,4
3
,,,,43
,,,,41
,,2
4
2
3
20
jii
jii
zjijzii
ij
zjiji
jzii
ijjijizjziijr
jijiij
D
IIeIIeIIIIe
IIIIeIIIIII
IDIH
ijijijij
ij
ij
ji
ijijijyji
ijijijxji
ijijzji
rr
rr
rr
sinsinˆ
cossinˆ
cosˆ
,,
,,
,,
Zero-quantum terms Single-quantum terms
Double-quantum terms
Principal-Axis System (PAS)
jijijizjzi
r
jijiij
D
IIIIII
IDIH
ij
ji )]([ ,,,,41
,,2
4 3
20
jijizjziijD
jijijizjziijDD
IIII
IIIIIIH
](3[
)]([2
,,,
,,,,41
,,,
2
2
2
2',2',2,'
)2( )0,,()1(m m
mD
mD
ijijmmm
jiD TDH
(dipolar tensor in PAS)
DD
rD
ij
ji
2,21,2
40,2
0
63
20
and spin part (operator tensor)
,,21
2,2
,,,,21
1,2
,,61
0,2
)(
)3(
jiD
jzizjiD
jizjziD
IIT
IIIIT
IIIIT
The most important terms are those commuting with i ziI ,
:
ji
jijizjziijr
D IIIIIIHij
ji )]()[1cos3( ,,,,41
,,2
4sec
3
20
2
2,20,2,0
)2( )0,,()1(m
mDD
ijijmm
jiD TDH
Expressed with irreducible tensors
Why irreducible tensors?
• Rotation is treated most conveniently by means of irreducible tensors
• No matter how many rotations you have, the calculation is straightforward if the Hamiltonian is expressed in terms of irreducible tensors.
2
2',,20,2,0
)2(',
)2( )0,,()0,,()1(mm
mDD
ijijmMrmmm
jiD TDtDH
PASRotorLAB
Electric quadrupolar interaction
For a quadrupolar nucleus (spin>=1), the electric field gradient (EFG) at the nucleus may cause energy shift for the nucleus.
The general form for EFG is a tensor (like dipolar coupling tensor).
r
EV
The quadrupolar Hamiltonian can be derived as
IVIIQIHIIQe
EQ )12(2
2
0
)]()1(3[ 22212
)12(4
2
zzyyxx
V
VVQ
QzIIQVe
Q
VVV
IIIIIH
zz
yyxx
zz
In the principal axis-system (PAS), it is given by
In arbitrary coordinate systems, electric quadrupolar interaction is given by
2
2
2
2',2',2,'
)2( ),,()1(m m
mQ
mQ
mmm
Q TDH
with spatial part (quadrupolar tensor in PAS):
QQQ
Q
QIIQVeQ
2,2
1,2
)12(40,2
0
66 332
and spin part (operator tensor)
IIT
IIIIT
IIIT
Q
zzQ
zQ
21
2,2
21
1,2
2
61
0,2
)(
)]1(3[
β
α
γ
Secular term (First order)
)]1(3)[2cossin1cos3({ 22221
)12(4sec 33
2
IIIH zQIIQVe
Q
For many quadrupolar nuclei, higher orders may becomeappreciable and need to be removed.
Chemical shift interaction
2
0 ',,',,'
)( ),,()1(k
k
kmmmk
CSmk
CSmm
kmCS TDH
)(
0
)(23
33221131
0
21
2,21,223
0,2
12131,1120,100,0
1122
033
1122
CSCS
CSCSCSCS
CSCS
CSCSCS ii
.0,,
,0,
2,2021
1,2032
0,2
021
1,10,1031
0,0
CSCSz
CS
CSCSz
CS
TBITBIT
BITTBIT
zCSCSCS IH )2cossin1cos3({ 2221
The most significant term is
J-coupling interaction
jijiij
J IJIH
2,0
2
2',,',,'
)( ),,()1(k mm
mkJ
mkJ
ijijijmmkm
jiJ TDH
The expression of J tensor is complicated and is not discussed here. Unlike direct dipolar interaction, J-coupling tensor has non-zero isotropic component and in most cases, it is the only term to be considered.
The most important internal interactions in NMR spectroscopy are
• Chemical shift interaction
• J-coupling interaction
• Dipolar coupling interaction
• Quadrupolar interaction
• Spin-rotation interaction (for rotating molecules, not studied here)
All of them can be written in the form of where R is a rank-2 tensor (matrix), varying with the type of interactions.
Coordinate Systems
Lab Frame(XYZ)
),,(
JQDCTRHk
k
kmmkmk ,,,
2
0,',
k
kmm
mkmmk
rMmmkm
mk DtDR",'
',,')(
',")(
, ),,(),,0()1(
How to calculate a solid NMR spectrum
JQDCTRHk
k
kmmkmk ,,,
2
0,',
),,,,,(
dteedddS titi ,,,
),,,,,(sin)(
More generally,
dteeeIdddS titiHtiH
,,,
),,,,,(),,,,,( ])0([sin)(
Chemical shit anisotropy interaction
Direct Dipole-Dipole Coupling
Spin Pair
~80 kHz
Many coupled spins
Decoupling Sequences
• Hetronuclear decoupling:
CW
TPPM
• Homonuclear decoupling
WAHUHA
MREV
HR
CORY etc
CRAMPS (combination of rotation and multi-pulse spectroscopy
Indirect Spin-Spin Coupling
• In contrast to the direct, through space dipole-dipole coupling of two nuclear magnetic moments, the indirect spin-spin coupling interaction is mediated by the electrons of the intervening bonds.
• The isotropic J coupling constant is familiar from solution NMR. We are also interested in anisotropies in the indirect spin-spin coupling tensor, denoted as J. This anisotropy can be measured by a few different techniques; solid-state NMR is especially useful in certain cases.
• Wasylishen J. Am. Chem. Soc. 2000, 122, 3197. • "Anisotropy in the 199Hg-31P Indirect Spin-Spin Couplin
g Tensor of a 1:2 Mercury-Phosphine Complex. A Phosphorus Single-Crystal NMR Study", Michael D. Lumsden, Roderick E. Wasylishen, and James. F. Britten J. Phys. Chem. 1995, 99, 16602.
Dipolar-Chemical Shift NMR (1D)• The interplay of
chemical shift anisotropy and spin-spin coupling interactions results in complex line shapes.
• The dipolar-chemical shift method is useful in the case of isolated spin pairs.
Many other cases where more than one interaction are involved.
Cross polarization• CP condition: The nutation frequen
cy must be the same for the two coupled spins:
• CP incorporated with MASCPMAS—one of the most important solid state NMR techniques.
• CP contact time: several hundred microseconds to tens of milliseconds.
• Purpose: To enhance the sensitivity of the lower γ spins such as carbon-13. maximal enhancement factor: γI/γS
• Other advantages: Shorter recycle delay time
• Distinguish the interconnectivity of nuclear spins such as the protonation of a certain carbon nucleus.
SI ,1,1
H B11H XB1 X
Separation of Local Fields
Chemical shift correlation
Chemical shift -dipolar correlation
Chemical shift-quadrupolar correlation
t1 tm t2I
S
Interaction A Interactions B,AMixing
Chemical Shift Correlation Spectrum
3D CSA-D Correlation (with One Quadrupolar Spin)
MQMAS
rfQJDCSAB HHHHHHH
ZB SH SH rf 1
)1()0(QQQ HHH
QQQQ
IIqQe
QnnmMRmj
nm
Qj
QQZ
QQZZQ
ZQ
Q
jDtDV
VVSS
VVSSSH
SSSVH
L
2222)12(820
222
2
2,2
222222
2121222)1(
2203
2)0(
,66
2,1,0,),,()0,,(
])122
)184[(
)]1(3[
2
Under rapid magic angle spinning (MAS):
)](cos)(),(
)(cos)(),()([
444
22200
2
MS
MSS
II
PICA
PICAICAL
Q
Dig EFGs From This Spectrum!
Energy Levels of a Spin-3/2 Nucleus in a Static Magnetic Filed
m3/2
1/2
-1/2
-3/2
Zeeman Quadrupolar (first-order)
Quadrupolar (second-order)
Quadrupolar Coupling May Be Very Strong! Multiple SitesMultiple Sites
In A PowderIn A Powder
)](cos)(),(
)(cos)(),()([
444
22200
2
PICA
PICAICAS
SSII L
Q
)](cos)(),(
)(cos)(),()([
444
22200
2
PICA
PICAICAS
SSII L
Q
Both The EFG Information And High Resolution Can Be Achieved.
Second Order Quadrupolar FrequencySecond Order Quadrupolar Frequency Second Order Quadrupolar FrequencySecond Order Quadrupolar Frequency
2D Solution:Keep AND Remove2D Solution:Keep AND Remove2D Solution:Keep AND Remove2D Solution:Keep AND Remove0)74.54(cos2 oP 0)74.54(cos2 oP
]0,0[])(cos)()(cos)(
,)(cos)()(cos)([
24241414
22221212
tPICtPIC
tPICtPIC
MS
MS
MS
MS
)()(/ 142421 ICICtt SS )()(/ 142421 ICICtt SS
Excitation Evolution Conversion Acquisition
P1 t1 P2 t2
θM θM
MQC SQC Magic AngleMagic Angle
(54.7 ) Spinning(54.7 ) Spinning
oo
Multi-Quantum Magic-Angle Spinning (MQMAS)
L.Frydman, J.S.Harwood, JACS, 1995.L.Frydman, J.S.Harwood, JACS, 1995.
2D-17O-DAS spectrum of the silicate coesite
MQMAS Signal Enhancement
S.Ding,C.A.McDowell, Chem. Phys. Lett. 1997, 270, 81-86.S.Ding,C.A.McDowell, Chem. Phys. Lett. 1997, 270, 81-86.
Other Topics
• Multiple pulse for homonuclear decoupling (WAHUHA, MREV, HR, CORY etc)
• Combination of rotation and multiple pulses (CRAMP)
• Recoupling (Rotational Resonance, REDOR, RFDR etc)
• Other multi-dimensional solid state NMR (HETCOR, CSA/Q correlation, D/Q correlation, 3D correlation spectra)
• Single-Crystal NMR
Effect of MAS on dipolar coupling
Proton Decoupling
Pulsed decoupling (WAHUHA, MREV-8)
Correlation experiment
Homonuclear correlation
Homonuclear correlation : establishing connectivities
• Let us have a tour of solid state NMR following Professor Malcolm H. Levitt.