the physical methods in inorganic chemistry (fall term, 2004) department of chemistry national sun...
TRANSCRIPT
![Page 1: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/1.jpg)
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
![Page 2: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/2.jpg)
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
![Page 3: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/3.jpg)
Single Crystal or Polycrystalline (Powder) Samples
![Page 4: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/4.jpg)
![Page 5: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/5.jpg)
Spin 1 creates a tiny magnetic field at spin 2 and vise versa, introducing direct magnetic coupling between them.
![Page 6: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/6.jpg)
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
![Page 7: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/7.jpg)
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
,,,,,,
,,,,,,,,,
,,,,,,,,,
,
,
![Page 8: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/8.jpg)
]))((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
,,,,,,,,,
,,,,,,,,,
,,,,,,,,,
![Page 9: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/9.jpg)
)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.
![Page 10: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/10.jpg)
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
![Page 11: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/11.jpg)
Spherical Coordinates
cos
sinsin
cossin
rz
ry
rx
(x,y,z)
r
![Page 12: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/12.jpg)
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
![Page 13: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/13.jpg)
Principal-Axis System (PAS)
jijijizjzi
r
jijiij
D
IIIIII
IDIH
ij
ji )]([ ,,,,41
,,2
4 3
20
jijizjziijD
jijijizjziijDD
IIII
IIIIIIH
](3[
)]([2
,,,
,,,,41
,,,
![Page 14: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/14.jpg)
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
![Page 15: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/15.jpg)
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
![Page 16: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/16.jpg)
![Page 17: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/17.jpg)
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
![Page 18: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/18.jpg)
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
![Page 19: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/19.jpg)
![Page 20: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/20.jpg)
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
![Page 21: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/21.jpg)
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.
![Page 22: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/22.jpg)
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
![Page 23: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/23.jpg)
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.
![Page 24: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/24.jpg)
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.
![Page 25: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/25.jpg)
![Page 26: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/26.jpg)
Coordinate Systems
Lab Frame(XYZ)
),,(
JQDCTRHk
k
kmmkmk ,,,
2
0,',
k
kmm
mkmmk
rMmmkm
mk DtDR",'
',,')(
',")(
, ),,(),,0()1(
![Page 27: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/27.jpg)
How to calculate a solid NMR spectrum
JQDCTRHk
k
kmmkmk ,,,
2
0,',
),,,,,(
dteedddS titi ,,,
),,,,,(sin)(
More generally,
dteeeIdddS titiHtiH
,,,
),,,,,(),,,,,( ])0([sin)(
![Page 28: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/28.jpg)
Chemical shit anisotropy interaction
![Page 29: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/29.jpg)
Direct Dipole-Dipole Coupling
Spin Pair
~80 kHz
Many coupled spins
![Page 30: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/30.jpg)
Decoupling Sequences
• Hetronuclear decoupling:
CW
TPPM
• Homonuclear decoupling
WAHUHA
MREV
HR
CORY etc
![Page 31: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/31.jpg)
CRAMPS (combination of rotation and multi-pulse spectroscopy
![Page 32: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/32.jpg)
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.
![Page 33: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/33.jpg)
![Page 34: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/34.jpg)
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.
![Page 35: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/35.jpg)
![Page 36: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/36.jpg)
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
![Page 37: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/37.jpg)
![Page 38: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/38.jpg)
Separation of Local Fields
Chemical shift correlation
Chemical shift -dipolar correlation
Chemical shift-quadrupolar correlation
t1 tm t2I
S
Interaction A Interactions B,AMixing
![Page 39: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/39.jpg)
Chemical Shift Correlation Spectrum
![Page 40: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/40.jpg)
3D CSA-D Correlation (with One Quadrupolar Spin)
![Page 41: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/41.jpg)
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
![Page 42: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/42.jpg)
Under rapid magic angle spinning (MAS):
)](cos)(),(
)(cos)(),()([
444
22200
2
MS
MSS
II
PICA
PICAICAL
Q
![Page 43: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/43.jpg)
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
![Page 44: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/44.jpg)
)](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
![Page 45: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/45.jpg)
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)
![Page 46: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/46.jpg)
L.Frydman, J.S.Harwood, JACS, 1995.L.Frydman, J.S.Harwood, JACS, 1995.
![Page 47: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/47.jpg)
2D-17O-DAS spectrum of the silicate coesite
![Page 48: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/48.jpg)
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.
![Page 49: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/49.jpg)
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
![Page 50: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/50.jpg)
Effect of MAS on dipolar coupling
![Page 51: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/51.jpg)
Proton Decoupling
![Page 52: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/52.jpg)
Pulsed decoupling (WAHUHA, MREV-8)
![Page 53: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/53.jpg)
Correlation experiment
![Page 54: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/54.jpg)
Homonuclear correlation
![Page 55: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/55.jpg)
Homonuclear correlation : establishing connectivities
![Page 56: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/56.jpg)
![Page 57: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/57.jpg)
• Let us have a tour of solid state NMR following Professor Malcolm H. Levitt.
![Page 58: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/58.jpg)
![Page 59: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/59.jpg)
![Page 60: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/60.jpg)
![Page 61: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/61.jpg)
![Page 62: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/62.jpg)
![Page 63: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/63.jpg)
![Page 64: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/64.jpg)
![Page 65: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/65.jpg)
![Page 66: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/66.jpg)
![Page 67: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/67.jpg)
![Page 68: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/68.jpg)
![Page 69: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/69.jpg)
![Page 70: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/70.jpg)
![Page 71: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/71.jpg)
![Page 72: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/72.jpg)
![Page 73: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/73.jpg)
![Page 74: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/74.jpg)
![Page 75: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/75.jpg)
![Page 76: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/76.jpg)
![Page 77: The Physical Methods in Inorganic Chemistry (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](https://reader038.vdocument.in/reader038/viewer/2022102417/56649cd75503460f9499fa2d/html5/thumbnails/77.jpg)