Ber$lHalle,LundUniversity,Sweden

Anuclearmagne,cmomentinteractswiththemagne,celdBatitsposi,on
externalsta,c polariza,on
externalradiofrequencymanipula,on
internaluctua,ngrelaxa,on

B(t) = B0 + B1(t) + b(t)

AmomentprecessesaroundBwithangularfrequency:

= B = B0 + bz = 0 + int
Eachspinprecessesataslightlydierentfrequency
dephasingandlossoftransversemagne,za,on

Thermalmolecularmo,on internaleldb(t)uctuates.
Ifb(t)reversesrandomly,onaverageevery10ps(=correla,on,me,c),then
(inaframerota,ngat0)willprecessbackandforthinverysmallsteps.
Forb0=5G,int105s1andintc=106rad.
Meansquareangulardisplacement
aXerN=t/csteps:

bz
b0

2
( )2 = N ( int c )2 = int
c t

t/c

b0

/(intc)

Dephasingofmomentslossof
transversemagne,za,onon,me
scaleT2when<2>1/2=1radian:

/(intc)

t/c

t/c

R2

1
2
= int
c
T2

R2=transverserelaxa,onrate
(T2=10sinourexample)

Rstatic = int

2
R2 = int
c

Inthelimitc0,thereisnorelaxa,on(R2=0).Themomentsthenseetheaverage
internaleld,<b>=0.Hencenodephasing.
Inthelimitc(nomolecularmo,on),theinternaleldissta,cbutinhomogeneous.
Thetransversemagne,za,onisthendephasedatarateRsta,c.
Thiscoherentdephasingprocessisreversible;itcanbeundone(byaspinecho).
Incontrast,theincoherentdephasingdescribedbyR2isirreversible.
[Why?Becausewearetooclumsytoreversethemolecularveloci,es.]

TheexpressionforR2isvalidwhentheangularstepsaresmall:

int c < 1

or

c < T2

Thisdenesthemo,onalnarrowingregime(sincelinewidthR2).

Theinternaleldcomponentbz(parallelwithB0)inducestransverserelaxa,on(dephasing).
Thecomponentsbxandbyinducebothtransverseandlongitudinalrelaxa,on.
Theinternaleldseenbyanuclearmomentisproducedbyothernearbymoments.
PrecessionofthesemomentsintheB0eldpartlyaveragesbxandby(butdoesnotaectbz).
Longitudinalrelaxa,oniscauseden,relybytheseprecessionaveragedcomponents:
xedc

R2
R1

0c
temperature

R1maximum
atc1/0

R1,R2

log(R1,R2)

xed0

R2
R1

0c
B0eldstrength

R1dispersion
at01/c

2
1
int
c
R1
=
T1
1 + ( 0 c )2

Longitudinalrelaxa,onrateR1
dependsonLarmorfrequency
andexternaleld(0=B0):
Magne,cRelaxa,onDispersion
IfLarmorprecessionismuch
slowerthanmolecularmo,on
itdoesnotaveragebx&by:

0 c << 1 R1 = R2
Extremenarrowingregime

Thespincouplingdenesa,mescale:1/int
100

spectraldriXinreal,me

intc

10

0.1

0.01

dynamiclineshapes
1storderinint

spinrelaxa,on
2ndorderinint

Eachcouplingdenesa,mescale:H=H0+Hint 1/0&1/int
100

intc

10

0.1

0.01
0.01

0.1

10

100

0c
Molecularmo,onsoccuronseveral,mescales(severalcs)

Molecularmo,onsareusuallydescribedbyclassicalmechanics,
whereasthespinsmustbetreatedquantummechanically.
SemiclassicalspinHamiltonian:

H (t) =

Aq (I ) Fq (x(t))
q

Incondensedphasesthemoleculesinteractstronglywitheachother,
somanymoleculardegreesoffreedom(dof)evolveinacoupledway.
Useacontracteddescrip,on,whereonlytherelevantdofx(t)istreated
explicitlyandalltheotherdofsaredescribedstochas,cally.
Intheend,weaverageovertheapparentrandomness(ensembleaverage).
Examples:chemicalkine,cs,Brownianmo,on.

Arandomvariable,x
maybecon,nuous,liketheorienta,onorlengthrofaninternuclearvector
ordiscrete,likeconforma,onalstatesorspa,alregions;
isdenedbytherangeofxandtheprobabilitydistribu,onP(x),where
P(x1)dx=probabilitythatx1+dx/2<x<x1+dx/2
Arandomprocess,x(t)
isthesetofpossiblerealiza,ons(ortrajectories)x(t)
whoseoccurrenceisdeterminedbyahierarchyof,medependent
jointprobabilitydensi,esP(x1,t1),P(x1,t1;x2,t2)etc.
Thecondi,onalprobabilityP(A|B)=probabilityofB,giventhatAoccurred.
AMarkovprocessisdenedby:

P(xn , t n | x1, t1, x2 , t2 ,..., xn1, t n1 ) = P(xn , t n | xn1, t n1 )

Asta,onaryrandomprocessisindependentof,meorigin(trueatequilibrium).
Asta,onaryMarkovprocessisdeterminedbytheequilibriumdistribu,onP(x)
andbythepropagatorP(x,|x0)=probabilityofhavingxat,givenx0at=0.

Asta,onaryMarkovprocesshasthefollowingproper,es(con,nuouscase):

P(x, | x0 ) 0
P(x, 0 | x0 ) = (x x0 )
P(x, | x0 ) = P(x)

dx P(x, | x0 )

=1

dx0 P(x0 ) P(x, t | x0 )

= P(x)

Asta,onaryMarkovprocesssa,sesthemasterequa,on(discretecase):

d
P(k, | m) =
d

[Wlk P(l, | m) Wkl P(k, t | m)]

l

Thephysicsentersviathetransi,onratesWkl.The,mereversibilityofthe
Newtonsequa,onsofmo,onleadstothedetailedbalancecondi,on:

Pl Wlk = Pk Wkl

ThesemiclassicalspinHamiltoniancontainsfunc,onsF(x(t))ofrandomprocessx(t).
Theensembleaveragethatlinkstherandomprocessx(t)thetospinrelaxa,onrates
isthe,me(auto)correla,onfunc,on(TCF):

G( ) = [F(x(0))]* F(x( )) =

dx0 dx P(x0) P(x, | x0) [F(x0 )]* F(x)

ThelimitsoftheTCFare:

G(0) =

F(x)

G( ) = F(x)

2
2

= 0

TheTCFisanevenrealvaluedfunc,on:

G( ) = G( ) = [G( )]*

TheTCFoXendecaysexponen,ally:

G( ) = G(0) exp
c
Evenwhenthisisnotthecase,
aneec,vecorrela,on,me
canbedenedas:

c d
0

G( )
G(0)

Spinrelaxa,onprobesmolecularmo,onsinthefrequencydomain.
Therelaxa,onrateR1thusinvolvesthespectraldensityfunc,on(SDF)J(),
whichistheFouriertransformoftheTCF:

1
J( )
d exp(i ) G( ) =
2

TCF

d cos( ) G( )
0

SDF(linear)

SDF(semilog)

J()/G(0)[ns]

G()/G(0)

J()/G(0)[ns]

10ns

10ns

3ns

3ns

[ns]

[108rads1]

[rads1]

R1( 0) = 2 [0.2 J( 0) + 0.8 J(2 0)] 2 J ( 3 0 )

Exponen,alTCFLorentzianSDF:

J( ) =

R1(0)

R1(0)

MRDprolesforc=50ns

MRDproleR1()SDFJ()

c
1 + ( c )2

Frequencyathalfamplitude:
0(MHz)

0(Hz)

T1(0)

R1(0)

1/2

Frequencyatinec,onpoint:

infl
0(Hz)

1
11.1 c

0(Hz)

1
20.9 c

modulatesallmoleculexedanisotropicspincouplings

free,isotropicdiusion
J( ) =

R
1 + ( R )2

R =

c V 0
kB T

free,anisotropic(symmetrictop)diusion
J( ) = A1

R1
R2
R3
+
A
+
A
2
3
1+ ( R1 )2
1 +( R2 )2
1 +( R3 )2

uniaxiallyrestricted,anisotropicdiusion
J( ) =

Ak

k =1

Rk
1 + ( Rk )

1 S2

) 1 + (
eff

eff )

TheproteinBPTIformsacompactdecamer
stabilizedbyspecicanioninterac,ons.

10 P P10
Thedecamerisiden,edfromitsR
anditspopula,onisobtainedfrom
theassociated1HMRDamplitude:

R1
R10
J( ) = G(0) x1
2 + x10
1+
(

)
1 +( R10 )2

R1

Gooschalk,Venu&BH,BiophysJ84,3941(2003)

canmodulatebothintraandintermolecularspincouplings

DT

Surface(2D)diusion

(transla,onallymediatedrota,on)

J( ) =

RT
1 + ( RT )2

RT

1
6 DT
+
R
R2

RelaDvediusionin3D
DT
DT
b

16 T
1+ /4
J( ) =
Re

; =
3
2
27 b
1 + + (4 + ) /9

b2
i T ; T =
2 DT

Dynamicaldisorderatthelevel
ofmolecularorspindynamics:

ExchangebetweenstateswithdierentR
(RB<<RA)

R ((t)) or R1((t))

eff
1 + ( eff )2
1
1
=
+
RA
A

J( ) =

(t)=discreterandomprocess

eff

A
RA

R1AA

Solidsubstrate(RA):EMOR

ExchangebetweenstateswithdierentR1
(fA<<1,R1A>>R1B)
R1( 0) =
R1

fA
+ fB R1B
+ 1/ R1A( 0)

Fastexchangelimit:R1AA<<1:
0(Hz)

R1( 0) = fA R1A( 0) + fB R1B

R1A
A

R1B
B

TheTCFoXendependson2ormorerandomprocesses,e.g.abivariateprocess{x(t),y(t)}:

G( ) = [F(x(0), y(0))]* F(x( ), y( ))

=

dx0 dy0 dx dy P(x0 ,y0) P(x, y, | x0 ,y0) [F(x0 ,y0 )]* F(x,y)
Theprocessesx(t)andy(t)arestaDsDcallyindependentif

P(x, y, | x0 ,y0) = P(x, | x0) P(y, | y0)

Theprocessesx(t)andy(t)areDmescaleseparated(withxmuchfasterthany)if

P(x, | x0) (y y0) for < *

P(x, y, | x0 ,y0) =
for > *
P(x) P(y, | y0)
Timescalesepara,onissucient,butnotnecessary,forsta,s,calindependence.

Iftheprocessesx(t)andy(t)aresta,s,callyindependentandifF(x,y)=Fx(x)Fy(y),then

G( ) = Gx ( ) Gy ( )
Letx=Lbeaorienta,onallyrestrictedlocalmo,onandy=Oanisotropicoverallmo,on.
Thedegreeofrestric,onisdescribedbyanorientaDonalorderparameterS,denedthrough

G ()
S L

GL (0)

1/2

ThereducedTCFcanbeexpressedintermsoftheorderparameteras

G( )
G ( )
= (1 S 2 ) G L ( ) + S 2 G O ( )
G(0)

Iftheinternalmo,onissucientlyfast,I<<O,1/0,then

J( )
O
J( )
= (1 S 2 ) L + S 2
G(0)
1 + ( O )2

GL ( ) S 2
d G L ( ) = d

2
1

0
0

MRDprolesfromcomplexsystemsareoXenmuchwiderthanaLorentziandispersion.
Ifaspecicdynamicmodelisnotavailable,suchstretchedprolesmaybemodeled
intermsofadistribu,onofcorrela,on,mes:
c
J(

)
=
G(0)
d

f
(

)
Inprinciple,thecdistribu,oncanbe
c c 1 + ( c )2
obtainedfromtheinversetransform:

f ( c ) =

2
2 Im{J( = i / c )}
c

But,inprac,ce,inevitabledataerrors
producetoomuchnumericalinstability.

Amoreprac,cal,butlessambi,ous,approachisto
toextractthemeansquareuctua,onamplitude

2
= G(0) = d J( )
0

andtheaveragecorrela,on,me

c =

R1(s1)

J(0)
G(0)

ThisMRDdatamustthenextendtohigh.

0(Hz)