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Phase Cycling and Gradient Pulses - The James Keeler Group

Phase Cycling and Gradient Pulses - The James Keeler Group

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1<br />

0<br />

–1<br />

–y<br />

t 1 τ m<br />

t 2<br />

<strong>and</strong> I –<br />

1<br />

cosΩt ( I + I )<br />

9–14<br />

2 1<br />

+ −<br />

Of these operators, only I –<br />

leads to an observable signal, as this corresponds to<br />

p = –1. Allowing I –<br />

to evolve in t 2<br />

gives<br />

( ) −<br />

cosΩt exp iΩt I<br />

1<br />

2 1 2<br />

<strong>The</strong> final detected signal can be written as<br />

1<br />

S t , t cosΩt exp iΩt<br />

C<br />

( )= ( )<br />

1 2<br />

2 1 2<br />

This signal is said to be amplitude modulated in t 1<br />

; it is so called because the<br />

evolution during t 1<br />

gives rise, via the cosine term, to a modulation of the<br />

amplitude of the observed signal.<br />

<strong>The</strong> situation changes if we select a different pathway, as shown opposite.<br />

Here, only coherence order –1 is preserved during t 1<br />

. At the start of t 1<br />

the<br />

operator present is –I y<br />

which can be written<br />

( )<br />

1<br />

−<br />

2i<br />

I+ − I−<br />

Now, in accordance with the CTP, we select only the I –<br />

term. During t 1<br />

this<br />

evolves to give<br />

( ) −<br />

exp iΩt I<br />

1<br />

2i<br />

1<br />

Following through the rest of the pulse sequence as before gives the following<br />

observable signal<br />

( )= ( ) ( )<br />

1<br />

SP t1, t2<br />

exp iΩt exp iΩt<br />

4 1 2<br />

This signal is said to be phase modulated in t 1<br />

; it is so called because the<br />

evolution during t 1<br />

gives rise, via exponential term, to a modulation of the<br />

phase of the observed signal. If we had chosen to select p = +1 during t 1<br />

the<br />

signal would have been<br />

( )= ( ) ( )<br />

1<br />

SN t1, t2<br />

exp –iΩt exp iΩt<br />

4 1 2<br />

which is also phase modulated, except in the opposite sense. Note that in either<br />

case the phase modulated signal is one half of the size of the amplitude<br />

modulated signal, because only one of the two pathways has been selected.<br />

Although these results have been derived for the NOESY sequence, they are<br />

in fact general for any two-dimensional experiment. Summarising, we find<br />

• If a single coherence order is present during t 1<br />

the result is phase<br />

modulation in t 1<br />

. <strong>The</strong> phase modulation can be of the form exp(iΩt 1<br />

) or<br />

exp(–iΩt 1<br />

) depending on the sign of the coherence order present.<br />

• If both coherence orders ±p are selected during t 1<br />

, the result is amplitude<br />

modulation in t 1<br />

; selecting both orders in this way is called preserving<br />

symmetrical pathways.<br />

9.4.2 Frequency discrimination<br />

<strong>The</strong> amplitude modulated signal contains no information about the sign of Ω,

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