NMRの信号がはじめて観測されてから47年になる。その後、NMRは1960年前半までPhys. Rev.等の物理学誌上を賑わせた。1960年代後半、物理学者の間では”NMRはもう死んだ”とささやかれたということであるが(1)、しかし、これほど発展した構造、物性の

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1 4. [] H Ψ Ψ u Ψ= cu, cc = (4..) A A m, m m < A>=< Ψ A Ψ >= c c < u A u > (4..) c A (4..)Ac m c c AA m m c c c c c m (4.. ) c c P < P m >= cmc m m, (4..3) < A >= < P m >< u A u > = Tr( PA) (4..4) m A P (3.3.) dc d = < u H ul > cl l

2 4. 4 d < P m >= < HP PH m >= < [ H, P] m > d (4..5) < u A u > c c m m m c c =< ρ m > (4..6) ρ desy marx < A > = Tr{ ρ A} (4..7) Tr Trace A < A > H (4..)u H cc E Z e = (4..8a) Z = E Z e (4..8b) c = c e α (4..9) ( m) m = m c c c c e α α (4..) radom phase approxmao E e cmc = ( ρ m) = δm (4..) Z

3 4 H e ρ = (4..) H Tre α α m ρ m m (4..) d ρ = [ H, ρ ] d (4..3) (3.3.3) vo Neuma Neuma Louvlle Louvlle-vo Neuma U ρ() = U() ρ() U () + (4..4a) U () = (4..4b) d U () = HU () () d U ( ) = Texp{ H ( ) d } (4..5) T Dyso me-orderg operaorexp U propagaor H (4..3) H H ρ( ) = exp( ) ρ()exp( ) (4..6) (3.4.)H

4 4. 43 H ()ρh H H ρ ( ) = exp( ) ρ( )exp( ) (4..7) H H H( ) = exp( ) Hexp( ) (4..8) d ρ d = [ H, ρ ] 4..9) ρ () ρ () [ ('), ρ (')] d ' (4..) = + H ρ () ρ ( ) ρ () ρ ( ) ρ ( ) ρ ( ) ρ () [ ( '), ρ ()] ' ( ) [ ( '),[ ( ''), ρ ()]] d' d'' (4..) ' = + H d + H H ρ ( ) d ρ ( ) = [ ( ), ρ ()] + ( ) [ ( ),[ ( ), ρ ()]] d (4..) d h h H H H H k = m = k < ρ() m >=< ρ () m >= (4..3) < k ρ() k >=< k ρ () k >= (4..4) d < m ρ( ) m > k m d d d < m ρ m >= < m ρ m >= < m [ H, ρ ()] m > d d + ( ) < m [ H ( ),[ H ( '), ()]] m > d' ρ (4..5)

5 44 m k d < m ρ m >= ( ) { < m H( ) k >< k H( ') m > d +< m H ( ') k >< k H ( ) m > } d' Em Ek < m H( ) k >=< m H( ) k > exp( ) (4..6) (4..7) d Em Ek < m ρ m >= ( ){ < m H() k >< k H(') m > exp[ (' )] d Em Ek +< m H( ') k >< k H( ) m > exp[ ( ' )]} d' (4..8) ω H ( ) = { I+ exp( ω) + I exp( ω )} (4..9) (4..7) m = k + m = k m = k + E ( k+ E k = ) ω (4..3) d ω s( ω ω ) < k + ρ k + >= { I( I + ) k( k + )} d ω ω g( ω ) k k + ω s( ω ω ) k k+ = + + ω ω ω W {( I I ) k( k )} g( ) dω πω = {( I I + ) k( k + )}( g ω) (4..3) (3.4.) (4..3) 4. NI

6 4. 45 B TM H N = γ I B = ρ = Tr N M = γ I = H H exp( ) {exp( )} I m > m, m, m3, m N >. < M >= Tr{ ρ M} = Tr{exp( γi B / )} γi / Tr{exp( γ I B / )} exp Tr{ + γ I B / + } = = ( I + ) Z I I I m= I m = I mn= I M XY Z γi B γ jz γ j Tr{( + / + ) I } = {( ) B / } Tr{ I I } I I N B IZ m= I m= I mn = I = {( γ ) / }{ I I N I I N IZ INZ m= I m= I mn= I m= I m= I mn= I + + } I( I + )(I + ) = {( γ ) / } ( + ) 3 M N B N I N( γ ) I( I + ) B =< MZ >= 3 < M >=< M >= X Y N j Z jz (4..) H

7 46 M = χ H m χ magec suscepbly m N( γ ) I( I + ) χ m = µ 3 (4..) 4. 3 FID 9 o H 9 o X ω ω ω H = ωiz + ω( e I+ + e I ) Louvlle-vo Neuma dρ = [ H, ρ] d σ = exp( ωi ) ρexp( ωi ) Z Z x σ dσ = ( ω ω)[ Iz, σ] ω[ Ix, σ] = [ Hro, σ ] (4.3.) d H ro = ( ω ω) I z + ω I x ω = ω σ ( ) = exp( ω I ) σ()exp( ω I ) x x σ H exp( ) () () γ I ( z B = ρ = = + ) H (I + ) Tr{exp( } (4.3.)

8 4. 3 FID 47 γ B σ() = { + ( Iz cos ω) Iy s ω )} (I + ) 9 o γ π ω = 9 o γ γ γ B σ ( + ) = ( + I y ) (I + ) γ zy9 o H = ω I Z γ γ B ρ( ) = exp( ωiz) σ( + )exp( ωiz) = { + ( IY cosω IX s )} (I + ) γ ω N I X γ NI( I + )( γ ) B γ M X () = NTr{ γixρ()} = sω = Msω (4.3.3) γ 3 γ X (4.3.) I z ρ () = I z (4.3.4) X γb Ho Ho γb ρ ( ) = exp( ) IX exp( ) = IX ( ) (I + ) (I + ) I X () X ( γ ) X = γ Xρ = X X B H H M () NTr{ I ()} N Tr{ I exp( ) I exp( )} (I + ) ( γ) B ( γ) B = N TrI { X ( I ) X ()} = N < IX ( I ) X () > (I + ) µ (4.3.5) (4.3.5)

9 48 NB MX () = < µ X () µ X () > X X 4. 4 Louvlle-vo Neuma Søreseproduc operaor []B s [] σ () = bs() B S (4.4.) S / NSørese produc operaor 4 N B S N ( q ) = ( ) sk (4.4.) k= a I κν ν xyzq / a qa=n q B s N Tr( B B ) = δ N r s rs (4.4.3) N= Ix Iy Iz (4.4.4) (x) =6 q= (/) q= I x, I y, I z, I x, I y, I z q= I x I x, I x I y, I x I z, I y I x, I y I y, I y I z, I z I x, I z I y, I z I z (4.4.5) I kx I k x

10 I ky I k y I kz I k z I kx I lz I k I l x I kx I lx, I kx I ly, I ky I lx, I ky I ly I k I l I kz I lz I k I l (xx) =64 4I x I x I 3x combao le exp( H) Bs exp( H) = bs ( B ) (4.4.6) ro k H = ω k k H = ωkikz I ν / J H = Jkl Ikz Ilz QIz H = ω I H = ω ( I cosδ + I s δ) x y δ x σ ( + ) = exp{ ω ( I cosδ + I s δ)} σ( )exp{ ω ( I cosδ + I s δ )} x y x y β β = ω δ = xγ β x β β -xδ = π, π, 3π

11 5 β -y β x β y β x β -x exp( β I ) I exp( β I ) = I x x x x exp( β I ) I exp( βi ) = I cos β + I s β x y x y z exp( β I ) I exp( βi ) = I cos β I s β I x β I x x z x z y I (4.4.7a) x β I x y y z I I cos β + I s β (4.4.7b) β I x z z y I I cos β I s β (4.4.7c) β y β I y x x z I I cos β I s β (4.4.8a) I y β I y I (4.4.8b) y β I y z z x I I cos β + I s β (4.4.8c) β z β I z x x y I I cos β + I s β (4.4.9a) β I z y y x I I cos β I s β (4.4.9b) I z β I z I (4.4.9c) z β z δ β xyz z δ x β z δ β[ Ixcosδ+ Iys δ] β x z β δ x β δ δ y I I s s + I (cos s + cos ) + I s s δ (4.4.a) [ Ixcos Iys ] I β δ + δ β y Iz s β cosδ + Ix s s δ + Iy(cos β cos δ + s δ ) (4.4.b)

12 β[ Ixcosβ+ Iys δ] z z x y I I cos β + I s βsδ I s βcosδ (4.4.c) H = ω I + J I I (4.4.) k k kz kl kz lz k< l k (3.4.) exp( ω I ) I exp( ω I ) = I cosω + I sω k kz kx k kz kx k ky k ω I kx kx k ky k k kz I I cosω + I sω (4.4.a) ω I ky ky k kx k k kz I I cosω I sω (4.4.b) I kx I lx ( ω k I kz + ω l I lz ) [ ωkikz+ ωlilz] kx lx kx ωk ky ωk lx ωl ly l I I ( I cos + I s )( I cos + I s ω ) J / k l J (4.4.) [ JklIkzI ] cos( J lz kl Jkl Ikx Ikx ) + Iky Ilz s( ) (4.4.3a) [ JklIkzI ] J lz kl Jkl Iky Iky cos( ) Ikx Ilz s( ) [ JklIkzI ] cos( J lz kl Jkl Ikx Ilz Ikx Ilz ) + Iky s( ) [ JklIkzI ] J lz kl Jkl Iky Ilz Iky Ilz cos( ) Ikx s( ) (4.4.3b) (4.4.4a) (4.4.4b)

13 5 f( θ ) = exp( θi I ) I exp( θi I ) z z x z z θ f ( θ) = exp( θi I ) I I exp( θi I ) z I = 4 f ( θ ) = f( θ ) 4 z z y z z z θ θ f( θ ) = Acos( ) + Bs( ) B f() = A= Ix f () = = IyIz (4.4.3) (4.4.4) H = ω (3 I I I I ) D D z z 3IzIz I I = 3 IzIz {( I + I) I I } 3 = 3 IzIz F( F + ) + 4 c J = ω (4.4.5) 3 D J H ( ) 3 Q = ωq Iz I z x z f ( θ) = exp( θi ) I exp( θi )

14 df ( θ ) = exp( θiz )( Iz Ix + IxIz )exp( θiz ) = exp( θiz )( IyIz + IzIy)exp( θ Iz ) dθ d f( θ ) = exp( θi ){ {( ) ( ) }exp( ) z Iz IyIz + IzIy + IyIz + IzIy Iz θiz dθ (.3.3)I x d f( θ ) = exp( θ I ) exp( ) ( ) z Ix θiz = f θ dθ f( θ ) = Acosθ + Bsθ f() = A= Ix f () = B = ( I I + I I ) y z z y z x z x y z z y exp( θ I ) I exp( θi ) = I cos θ + ( I I + I I )sθ z y z y x z z x exp( θ I ) I exp( θi ) = I cos θ ( I I + I I )sθ ωqi z x x ωq y z z y I I cos + ( I I + I I )sω (4.4.6a) Q ωqiz y y Q x z z x I I cos ω ( I I + I I )s ω Q (4.4.6b) ωqiz y z z y y z z y ωq x ωq ( I I + I I ) ( I I + I I )cos I s (4.4.6c) ωqiz x z z x x z z x ωq y ωq ( I I + I I ) ( I I + I I )cos + I s (4.4.6d) / J Mahemaca POMA

15 54 [4] ) C. Kel, Elemeary Sascal Physcs, Joh & Wley, New York, 958. ) O. W. Sørese, G. W. Ech, M. H. Lev, G. Bodehause, ad R. R. Ers, Progr. NMR Specroscopy 6, 63(983). 3) U. Fao, Rev. Mod. Phys. 9, 74(957). 4) P. Guer, N. Schefer, G. Og, ad K. Wührch, J. Mag. Reso., 3(993).

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No δs δs = r + δr r = δr (3) δs δs = r r = δr + u(r + δr, t) u(r, t) (4) δr = (δx, δy, δz) u i (r + δr, t) u i (r, t) = u i x j δx j (5) δs 2 No.2 1 2 2 δs δs = r + δr r = δr (3) δs δs = r r = δr + u(r + δr, t) u(r, t) (4) δr = (δx, δy, δz) u i (r + δr, t) u i (r, t) = u i δx j (5) δs 2 = δx i δx i + 2 u i δx i δx j = δs 2 + 2s ij δx i δx j

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