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 8. CW-NR Bloch[]Z (longitudinal relaxation timexy (transversal relaxation timebloembergen [] Bloch Bloembergen Bloch (3.. d d d x z = ( ω ω = ωz + ( ω ω x = ω ( z x (8..a (8..b (8..c = z = z θ = ω t ( ω θ = ω θ = ω ω = (8.. ω dx x = (8..3a dθ θ d = z+ x (8..3b dθ θ dz ( z = (8..3c dθ θ
2 8. CW-NR 95 x θ ( ω ω ω = = + θ + θθ + {( ω ω } + ω θ ω = = + θ + θθ + {( ω ω } + ω + θ + {( ω ω } = = + θ + θθ + {( ω ω } + ω z (8..a (8..b (8..c BX = B cosωt X Y = cosωt sinωt X x = sinωt+ cosωt Y x mh mh cosω ( ω ω ω χ ω χ X = t+ sinωt + {( ω ω } + ω + {( ω ω } + ω χ m (.. = χ H cosωt+ χ H sinωt (8..5 X χ χ χ = χ iχ ( ω ω ω χ = χm (8..6a + ({ ω ω } + ω ω χ = χm (8..6b + ({ ω ω } + ω dbx P = X = χ HBω + ω δ = 8.
3 96 8. χ χ χ χ CWcontinuous wave NR (8..cZω= ω ( + ω = = sec /=Hz.5 (8..6ω ω ωχm ( χ χ + ω + ω χ ω χ ( ( + m m ω + ω = (8..7 ω ( χ, χ 8. ωχ m + ω ωχ m + ω ωχm (, χ + ω
4 8. CW-NR 97 χ ωχ m χ = (8..8a + max ω χ = max ωχm + ω (8..8b ω χ χ χ 8. χ χ t = (8.. d x d d z = x = ωz = ω ( z x (8..9a (8..9b (8..9c
5 98 d = z (8..a dθ θ dz ( z = (8..b dθ θ ( z z / θ =, = 8. 3 θ 8. 3 z / θ = ( z θ = 8. NRBloch []Bloembergen [] Kubo omita[3] BPPSolomon [] Kubo-omitaRedfield
6 8. 99 [5]Redfield Kubo-omita-Redfield / αβ 8. n n W β 8. αβ n n ( α W α β ( β α dn α dn β = W n + W n ( α β α ( β α β = W n W n ( α β α ( β α β (8.. ( αβ W( β α W α β dn dn α β = = W W ( α β β W( α β = exp( γ B / k = W α ( β α n n W ( β α (8..
7 W W ( α β ( β α γ B = W( k γ B = W( + k n = n n α β dn = W( n neq (8.. = W (8..5 W BloembergenSolomon 8. 3 H H (t[5,6]h (t d ρ = [ H (, i t ρ ] (8.3. iht iht ρ = exp( ρexp( iht iht H = exp( H( texp( (8.3. t ρ( t = ρ( + [ H ( t, ρ( t ] (8.3.3 i ρ ( t ρ ( t = ρ ( + [ H ( t,{ ( [ H ( t, ( t ]}] i ρ + ρ (8.3. t t ih d ρ = [ H ( t, ρ (] + ( [ H ( t,[ H ( t, ( t ]] (8.3.5 i i t ρ
8 8. 3 H ( t = H (tρ( t t t = t τ τ d ρ t = dτ[ H( t,[ H( t τ, ρ ( t τ ]] (8.3.6 H (th (t-τττ τ t τ ρ ( t τ ρ ( t c d ρ = dτ[ H( t,[ H( t τ, ρ ( t] ] (8.3.7 ρ H (t G αα ββ G = H t H t (8.3.8 αα, ββ ( τ ( α ( α ( β ( τ β, ( τ τ j i j, ( G, ( e ωτ αα ββ ω αα ββ τ d d ρ = τ (8.3.9 i( α α β+ β t αα t = Rαα, ββ e ρββ ββ ( ( t (8.3. αα α R αα, ββ R αα, ββ = { j αβ, αβ ( α β + j αβ, αβ ( β α δβα j γβ, γα ( γ β δβα j βγ, αγ ( β γ} γ γ c (8.3. β β = α α (8.3.
9 d ρ αα t = Rαα, ββ ββ ββ ( ' ρ ( t (8.3.3 (8.3. d ρ αα t = Rαα, ββ ββ β ( ' ρ ( t (8.3. ρ αα, ββρββ Rββαα, ραα R αα = (8.3.5 R, = R, (8.3.6 ρ αα ββ ββ ραα ββ αα = (8.3.7 (8.3. ρ ( ρ ( t ββ ββ ρβ β ρ Eβ k e ββ = δββ Eγ k e γ (8.3.8 d ρ ( = ' ( ρ ( ρ (8.3.9 αα t Rαα, ββ ββ t ββ ββ master equationρ (8.3.(8.3.3 d i ρ ( [, ρ(] ' ( ρ ( ρ (8.3. αα t = H t αα + Rαα, ββ ββ t ββ ββ
10 A q= q ( q ( q H ( t = ( A ( t (8.. A ( q q ( q = ( A (8.. ( q + q ( q = ( (8..3 H q ( q ( q i ( t e α α = q ( α H α ( A ( t( α α ( q iht iht ( q ( q ( q i p t ( q ( = p, ωp = ω p p e e e ω q (8.. ( ( ( ( ( ( q q q q iw p t = p q p H t A t e (8..5 ( q ( q q ( q ( q q ( q τ δq q τ δq q A ( t A ( t+ = ( A ( t A ( t+ = ( c ( τ (8..6 (8..5(8.3.7 ρ ( ρ ( t ρ β d ρ p, ( q ( q q ( q p q p, ββ ββ β ( q iw '[,[,( ( t ]] ( c ( e p τ = ρ ρ τ dτ (8..7 ( q ( q p ' ωp + ω = ( q ( q iωτ J ( ω = c ( τ e dτ (8..8
11 ( q ( q i j ( ω = c ( τ e ωτ dτ (8..9 k ( q ( q ( ω = c sin( ωτ dτ (8.. ( ( ( j q ( ω = J q ( ω ik q ( ω d ρ q ( q ( q ( q ( q ( q ( q = '( [,[,( ( p ρ t ρ ]]{ J ( ωp ik ( ωp } (8.. q p, d ρ q ( q ( q ( q ( q = '( J ( ω [,[,( ( p p ρ t ρ ]] (8.. q p, B < B > = r{ ρ B} r{[ A,[ B, C]] D} = r{ C[ B,[ A, D]]} (8..3 (8.. (8.. B d ρ q ( q ( q ( q ( q r B = r{ '( J ( ω [,[,( ( p p ρ t ρ ]] B} (8..5 q p, d < B > = q ( q ( q ( q ( q r{( ρ ( t ρ '( ( [,[, ]]} J ωp p B q p, q ( q ( q ( q ( q b = '( J ( ω [,[, ]] p p B q p, (8..6 (8..7 < b > = r{ ρ b} (8..8a b = r{ ρ b} (8..8b d < B > = < ( b > b (8..9 BI Z z
12 5 F. Bloch, Phs. Rev. 7, 6(96. N. Bloembergen, E.. Purcell, and R. V. Pound, Phs. Rev. 73, 679(98. 3 R. Kubo and K. omita, J. Phs. Soc. Jpn. 9, 888(95. I. Solomon, Phs. Rev. 99, 559( A. C. Redfield, IB J. Res. Develop., 9( A. Abragam, he Principles of Nuclear agnetism, Clarendon Press, Oxford,
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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