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org/jchemeduc Article

Illustrating Elementary NMR Concepts through Simple Interactive

Python Programs
Ishita Sengupta*
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ABSTRACT: Introducing elementary concepts of nuclear magnetic resonance spectroscopy (NMR) to a beginner can be
challenging. Using an interactive graphical platform can greatly aid in demonstrating key concepts in such cases. This paper aims to
bridge this gap in teaching basic NMR spectroscopy through simple standalone interactive Python programs or a Jupyter notebook,
supplementing traditional theoretical approaches. These scripts allow the beginner with basic knowledge of quantum mechanics to
grasp important concepts like precession, nutation, laboratory and rotating frames, on- and off-resonance RF-pulses through user
input, and graphical and terminal output of results.
KEYWORDS: Upper-Division Undergraduate, Graduate Education/Research, Physical Chemistry, Computer-Based Learning,
NMR Spectroscopy

T he introduction of elementary NMR concepts to senior

undergraduate and first-year graduate students, with
experience in introductory quantum mechanics, has traditionally
been through theoretical approaches. A number of excellent
textbooks focusing on theoretical aspects of NMR spectroscopy
are available.1−3 In addition, many software programs for
calculating and visualizing spin dynamics for complicated pulse
sequences and some educational NMR software4 have also been
developed.5−9 However, these are most useful for advanced
researchers in the field and/or those who have a good handle on
the programming language; in addition, they are expensive and/
or noninteractive. Physical chemistry laboratory and computa-
tional exercises describing the fundamental aspects of pulsed
NMR10,11 and detection,12,13 computation of NMR spectra and
parameters,14−16 study of conformational equilibria,17 and
theoretical aspects of product operator formalism,18 the vector
approach,19 and multidimensional NMR,20 etc., have been
successfully implemented in the undergraduate/graduate
curriculum.
For a beginner, visualizing spin dynamics in the presence of an
external magnetic field and/or RF-pulses can often be
challenging. An interactive platform with minimal programming
knowledge can be beneficial to such students. With this in mind,
© 2021 American Chemical Society and
Division of Chemical Education, Inc.
1673
I present a set of interactive Python programs to introduce the
concepts of precession, nutation, and rotating-frame approx-
imation and to visualize the effect of on- and off-resonance RF-
pulses of varying phases, offsets, and durations on an isolated
spin 1/2 system, ignoring the effects of relaxation and coupling.
Users can change relevant parameters and observe their effects
on spin dynamics as graphical outputs. A preliminary knowledge
of quantum mechanics, especially the time-dependent Schrö-
dinger equation, is assumed. All operators are expressed in the
matrix representation, and ℏ is set equal to 1 for convenience in
all calculations. A brief mathematical background for each
section is provided in the Supporting Information. Importantly,
while these scripts supplement the traditional theoretical
approaches of introducing these concepts, they cannot replace
them in entirety.
Received: July 28, 2020
Revised: March 14, 2021
Published: March 31, 2021
https://doi.org/10.1021/acs.jchemed.0c01008
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Journal of Chemical Education pubs.acs.org/jchemeduc Article

π π π π π π π π
Figure 1. Isolated spin 1/2 in any arbitrary orientation: (A) | 0, 0⟩, (B) |π, 0⟩, (C) 2 , 0 , (D) 2 , , (E) π , , (F) |0, π⟩, (G) 2 , , and (H) 4 , .

■
2 2 4 4

SPIN-STATES AND SPIN ANGULAR MOMENTUM
OPERATORS
In NMR, the nuclear spin angular momentum is manipulated by
short weak radiofrequency (RF) pulses BRF and delays, in the
presence of an external strong magnetic field B0, to produce a
detectable signal, which is modulated by the local environment
around the spin. From careful analysis of the signal, information
about the structure and dynamics of the molecule can be
extracted. In this paper, preliminary NMR concepts will be
described for an isolated spin 1/2, ignoring the effects of
relaxation.
Spin-States
An isolated spin 1/2 (or its nuclear spin angular momentum)
pointing in any arbitrary direction can be represented in
spherical coordinates by the ket |θ, φ⟩ where
(Figure 1) and calculates the spin-state (eq 1) (Figure S1). Here,
I demonstrate how different combinations of θ and φ result in
different orientations of an isolated spin 1/2.22
The take home message: The |0, 0⟩ and |π, 0⟩ states are the |α⟩
and |β⟩ states, respectively. All other spin-states can be expressed
as a linear combination of the |α⟩ and |β⟩ states (see later). A
spin oriented in the same direction can correspond to different
values of (θ, φ). For example, spin-states |0, 0⟩ (Figure 1A) and |
0, π⟩ (Figure 1F) point along the +z-direction, whereas spin-
π
states |π, 0⟩ (Figure 1B) and π , 2
(Figure 1E) point along the
−z-direction, respectively. It should be noted that the arrowhead
is rotated by different angles in Figure 1A,F or Figure 1B,E,
respectively, corresponding to the different values of φ. In
π π π
contrast, spin-states 2 , 0 (Figure 1C), 2 , (Figure 1D), and
2

ij cos θ yz
j 2 z
π π π π π

|θ , ϕ⟩ = jjjj zz
, (Figure 1G) are in the xy-plane with , 0 and ,

z
j sin θ e iϕ zz
k {
2 (1)
Here, θ is the angle which the spin makes with the +z-axis, and φ
is the angle which its projection makes with the +x-axis.21 (Here,
the direction of +x to +y to −x to −y is anticlockwise. A negative
θ value should be avoided as it changes the direction of
rotation.)
Some representative examples of an isolated spin 1/2 pointing
2 4 2 2 2
pointing along the +x- and +y-direction, respectively. Students
should vary θ,φ to generate spin-states with arbitrary
orientations (Figure 1H) and note if the coefficients are real
or imaginary.
Spin Angular Momentum
The expectation or average values of the x-, y-, and z-
components of the spin angular momentum of a given spin-
state (Section S2 in Supporting Information) are calculated by
the program expectation-ang_mom.py. The user defines the

i1y
in specific directions are

|0, 0⟩ = jjj zzz

spin-state by specifying the values of θ and φ. The spin-state and

k0{
expectation values of Ix ,̂ Iy ,̂ and Iz ̂ are calculated and displayed

i0y
on the terminal/notebook.

|π , 0⟩ = jjj zzz
The take home message: Students should verify that a spin 1/

k1{
2 pointing along the ±x-, ±y-, and ±z-direction is an
eigenfunction of Ix ,̂ Iy ,̂ or Iz ̂ operators with an eigenvalue of
±0.5, respectively. Spin-states, oriented in any arbitrary
i yz
and

= jjj zz
π π

k 0.27 + 0.27i {
π π 0.92 direction, for, e.g., , (Figure 1H), are not eigenfunctions
, 4 4
4 4 of Ix ,̂ Iy ,̂ or Iz ̂ operators and have nonzero expectation values of
The program state.py takes as input (θ, φ) (in degrees) and the spin angular momentum ⟨Ix⟩ = 0.25, ⟨Iy⟩ = 0.25, and ⟨Iz⟩ =
outputs the direction of the nuclear spin angular momentum 0.35 along x-, y-, and z-directions, respectively (Figure S2). For
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i 0.71 zy i1y i0y

= jjj zz = 0.71jjj zzz + (0.71i)jjj zzz
k 0.71i { k0{ k1{
Table 1. Eigenfunctions and Eigenvalues of the of Ix ,̂ Iy ,̂ and Iz ̂ π π
,
Operators 2 2

Iz ̂ |α⟩ = = (0.71)|α⟩ + 0.71i)|β⟩

i zyz
1
Ix ̂ α±β =

= jjj
2

z
k {
Iz ̂ |β⟩ = Iy ̂
1
α±β = π π 0.97
2 ,

ij 1 yz i0y
6 6 +

= (0.97)jj zz + (0.22 + 0.13i)jjj zzz = (0.97)|α⟩

Ix ̂ |α⟩ = 1 0.22 0.13i
Iz ̂ α±β =

k0{ k1{
2

Ix ̂ |β⟩ = 1
Ix ̂ 2 α ± iβ =

Iy ̂ |α⟩ = Iy ̂
1
α ± iβ = + (0.22 + 0.13i)|β⟩
2

Iy ̂ |β⟩ = Iz ̂
1
α ± iβ = The take home message: The examples shown above are
2
superposition states of the |α⟩ and |β⟩ spin-states with
probabilities |C+|2 and |C−|2, respectively. The expectation
spin-states which are eigenfunctions of the Ix ,̂ Iy ,̂ or Iz ̂ operators, (average) value of the energy of a superposition state (which
the expectation values and eigenvalues are identical. Students is not an eigenvector of Ĥ ) is evaluated by calculating ⟨θ, φ|Ĥ |θ,
should also verify which spin-states are simultaneous eigenfunc- φ⟩ (eq S2). Students should verify that the average energy and
tions of the Ix ,̂ Iy ,̂ or Iz ̂ operators (Table 1). average z-component of the spin angular momentum ⟨θ, φ|Iẑ |θ,

■ ZEEMAN HAMILTONIAN AND SUPERPOSITION

STATES
Zeeman Hamiltonian and Superposition States
|θ, φ⟩ can be expressed in the Zeeman basis as a linear
combination of the |α⟩ and |β⟩ spin-states. The program
coefficients.py takes θ, φ (in degrees) as input, calculates the
coefficients C+ and C−, and outputs the user defined spin-state in
the Zeeman basis (Section S3 and Figure S3).
For example
φ⟩ of a superposition state are given by |C+|2E1 + |C−|2E2 and |
C+|2(0.5) + |C−|2(−0.5) where E1 and E2 are the energy
eigenvalues, and ±0.5 are the z-components of the spin angular
momentum corresponding to the |α⟩ and |β⟩ states, respectively
(see previous section). Students should also check if any
superposition state of their choice is an eigenfunction of the spin
angular momentum operators, Ix ,̂ Iy ,̂ and Iz ̂ (Table 1).
■ SPIN DYNAMICS
Precession

i 0.71 yz i1y i0y

= jjj zz = (0.71)jjj zzz + (0.71)jjj zzz
In the presence of an external magnetic field B0, a nuclear spin

k 0.71 { k0{ k1{

π undergoes precession about the B0 axis (z-axis) (Section S4 in
,0
2 SI). The program precession.py allows the user to specify the
initial state of the spin, the Larmor frequency, and the time
= (0.71)|α⟩ + 0.71)|β⟩ duration. It solves eq S4 to output the final polar coordinates of

π
Figure 2. (A−D) The initial state ψ(0), 2 , 0 (red arrow), precesses about the z-axis at a Larmor frequency 500 MHz for 0.25, 0.5, 0.75, and 1 ns to the
final state ψ(t) (orange arrow). (E−H) This is the same as in parts A−D except the Larmor frequency is 800 MHz. Note that, for the same time
intervals, the angle of rotation (ω0*t) for the spin is larger at 800 MHz compared to 500 MHz. Precession is equivalent to rotation about the z-axis.

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Figure 3. Rotation of spin-states: (A−C) The initial state |0, 0⟩ rotates by angle π about the axis defined by φp = 0 (x), π (y), and π (−x) resulting in the
final spin-states |π, 1.18π⟩, |π, 1.68π⟩ and states |π, 0.18π⟩, respectively. (D) The initial state |0, 0⟩ rotates by π about the axis defined by φp = 0 resulting
π 3π
in the final state 2 , 2
. (E) The initial state |π, 0⟩ rotates by π about the axis defined by φp = 0 resulting in the final state
2
π
2
, 0 rotates by π
about the axis defined by φp = 3π
resulting in the final state |0, 1.32π⟩.
2 2
the spin and graphically illustrates the initial and final spin-state.
Note that the time parameter here is just for the sake of
visualization. Since B0 is always “on” in an NMR experiment,
precession about the z-axis continues indefinitely. However, for
illustration purposes, precessions for different values of t have
been shown, to observe how the final spin-state changes during
precession (Figure 2).
The take home message: This section emphasizes the relation
among ω0, B0, γ, and ΔE between the |α⟩ and |β⟩ states for an
isolated spin 1/2. Students should calculate ω0 for an isolated
spin 1/2 with different γ values (corresponding to 1H, 13C, 15N,
19
F, 31P, etc.) and check for themselves how ΔE varies as a
function of B0. The examples shown here are for an isolated 1H
and illustrate the following: (1) The spin rotates through a larger
angle in the same amount of time with an increase in Larmor
frequency (Figure 2A−D versus Figure 2E−H). (2) By keeping
the Larmor frequency fixed and varying the time duration, the
angle of rotation can be varied (Figure 2A−D and Figure 2E−
H). Most importantly, students should note that precession
pertains to rotation about the z-axis, i.e., the B0 direction.
Rotation Operators
Experimentally, rotations of spin-states are realized by applying
weak RF-pulses away from the direction of B0 and treating the
problem in the rotating frame. Importantly, rotation can be
about any arbitrary axis and is fundamentally different from
precession, which is strictly about the z-axis.
The program theta_phi.py takes an isolated spin 1/2 pointing
in any arbitrary direction and operates Rφp(βp) on it (Section
S5). The initial state |θ, φ⟩, βp, and φp are taken as inputs. The
program outputs the initial and final state on the terminal/
console and graphically (Figure 3, and Section S5 and Figure
S5). The program also outputs the polar coordinates of the final
state |θ′, φ′ ⟩.
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2
2
3π 3 π
2
, 2 . (F) The initial state
The take home message: The |α⟩ state converts to the |β⟩ state
and vice versa upon rotation by 180° about the ±x-/±y-axis
(Figure 3A−C). In each case, the final state is |β⟩, but with a
different value of φ′ (corresponding to a different orientation of
the orange arrowhead). Spin orientations can be manipulated by
rotating about the appropriate axis and angle. For example, (i) a
rotation by 90° about the x-axis brings the |α⟩ state to point
along the −y-axis (Figure 3D) and the |β⟩ state to point along
the +y-axis (Figure 3E), and (ii) a rotation by 90° about the −y-
axis converts a spin pointing initially along the +x-axis to convert
into the |α⟩ state (Figure 3F). The right-hand thumb rule can
predict the final orientation of the spin after rotation and should
be verified with this program. Students should generate arbitrary
spin-states (superposition states) by changing the angle and axis
of rotation of their choice.
Rotating-Frame Approximation
The rotating-frame approximation simplifies the mathematics
(involved in solving eq S4) in the presence of a static magnetic
field B0 and an oscillating RF-pulse BRF. The program
rotating_frame.py calculates precession for a time duration
specified by the user at an offset Ω0, with ω0, ωref, and |θ, φ⟩
specified by the user (Figure 4, and Section S6 and Figure S6).
Precession in the laboratory frame (see above, eq S4, Figure
2) and precession in the rotating frame must be clearly
differentiated. For a spin with offset Ω0 = 0 Hz, there is no
precession. For the same duration, spins with varying offsets
rotate through different angles. This is equivalent to precession
in the laboratory frame, but in the presence of a reduced B0. The
sign of the offset specifies the direction in which the spin rotates.
For, e.g., a spin precessing at a Larmor frequency of 500 MHz in
the laboratory frame, this rotates by (i) an angle of 0° when the
offset = 0 Hz (Figure 4A), (ii) an angle of 18° when the offset =
105 Hz (Figure 4B), (iii) an angle of 180° when the offset = 106
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π
Figure 4. Precession in the rotating frame. The initial state 2 , 0 undergoes precession at ω0 = 500 MHz for 500 ns with (A) ωref = 500 MHz (Ω0 = 0
Hz), (B) ωref = 499.9 MHz (Ω0 = 1 × 105 Hz), (C) ωref = 499.0 MHz (Ω0 = 1 × 106 Hz), and (D) ωref = 500.1 MHz (Ω0 = −1 × 105 Hz) where ωref =
rotating-frame frequency and Ω0 = offset. Note the opposite direction of the final spin-state in the cases of examples B and D with offsets of equal
magnitude but opposite signs.

Figure 5. Graphical representation of an RF-pulse in the laboratory frame, with (A) ω1 = 2000 Hz, ωp = 50 MHz, and φp = 0 (x-pulse); (B) ω1 = 2000
Hz, ωp = 200 MHz, and φp = π (y-pulse); and (C) ω1 = 2000 Hz, ωp = 500 MHz, and φp = π . For an on-resonance pulse, ωp = ω0. The green asterisk
2 3
indicates the phase of the pulse, and the blue and red solid lines denote the x- and y-components of the oscillating RF field (shown as a gray solid line).

Hz (Figure 4C), and (iv) an angle of −18° when the offset =
−105 Hz (Figure 4D) in 500 ns.
The take home message: A spin with Larmor frequency ω0
equal to the rotating-frame frequency ωref has an offset Ω0 = 0
Hz. A difference in ω0 and ωref results in a positive or negative
value of Ω0. Opposite signs of Ω0 correspond to the opposite
directions of precession in the rotating frame (Figure 4B,D). In
the presence of the same external magnetic field B0, two spins
with identical γ values can have different magnitudes and signs of
offsets (corresponding to different ω0) modulated by the local
electronic environment around the spin. Students should realize
that, in an actual sample, more than one spin is present, with
different offsets. They should compare precession in the
laboratory and rotating frames for spins with different offsets
and/or time durations.
RF-Pulses
By applying weak oscillating radiofrequency fields away from the
z-axis, the spin can be rotated to different extents about different
axes. The RF-pulse.py program graphically illustrates the RF-
pulse, its x- and y-components, and the phase in the laboratory
frame. The user can interactively change all four parameters of
the pulse (Figure 5, and Section S7 and Figure S7). In Figure 5,
the amplitude of the pulse, B1, is kept fixed at 2000 Hz
(expressed in terms of ω1), whereas the phase and frequency are
set at 0 and 50 MHz (Figure 5A), π and 200 MHz (Figure 5B),
2
and π
and 500 MHz (Figure 5C), respectively.
3
The take home message: In the rotating frame, if the
frequency of the oscillating component of the RF-pulse (ωp) is
set equal to the rotating-frame frequency (ωref) and the Larmor
frequency (ω0), then the oscillating RF-pulse becomes a static
“on-resonance” RF-pulse. So, when both static magnetic field
and oscillating RF-pulse are present and ωref = ωp = ω0, then the
1677
spin only experiences the effect of the weak static RF-pulse
applied away from the z-axis and rotates about its axis in the
rotating frame. Students should change the phase, amplitude,
and frequency of the pulse and note how BRF changes with these
parameters.
Rotation in the Presence of On-Resonance RF-Pulses in the
Laboratory Frame (Nutation)
In the presence of B0 and BRF, the spin precesses fast about the z-
axis and slowly about the axis along which the pulse is applied.
The program nutation.py evaluates eq S10 with initial |θ, φ⟩,
Larmor frequency (ω0), rotating-frame frequency (ωref),
amplitude of the pulse in Hz (ω1), and time (tp) specified by
the user and outputs the nutation trajectory graphically (Figure
6 and Figure S8) and the final state on the terminal/notebook. In
each case, the initial and final states are identical (i.e., the flip
angles and phase of the pulses are kept constant), but the
nutation trajectories depend on the Larmor frequency (ω0)
(Figure 6A−C), the amplitude of the pulse (ω1) in Hz (Figure
6D,E), or both (Figure 6F).
The take home message: The flip angle of the pulse
determines the angle of rotation of the spin. However, both
the Larmor frequency (external magnetic field) and amplitude of
the pulse (in Hz) determine the spin dynamics in the laboratory
frame. Students should compare the nutation trajectories in the
presence of an offset (i.e., by setting ωref ≠ ω0) (off-resonance)
(Figure S8) with a trajectory when offset = 0 Hz (on-resonance)
(Figure 6).
Rotation in the Presence of On-Resonance RF-Pulses in the
Rotating Frame
The effect of an on-resonance RF-pulse in the rotating frame (ω0
= ωref = ωp) is to rotate a spin through a flip angle = ω1*τp around
the axis of the pulse. Since the problem is set in the rotating
frame, and the rotating-frame frequency is set equal to the
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Figure 6. Nutation of an isolated spin 1/2 during a π x-pulse for different values of ω0 and ω1 (A) ω0 = 250 MHz, ω1 = 500 Hz, t = 0.0005 s; (B) ω0 =
2
500 MHz, ω1 = 500 Hz, t = 0.0005 s; (C) ω0 = 1000 MHz, ω1 = 500 Hz, t = 0.0005 s; (D) ω0 = 600 MHz, ω1 = 250 Hz, t = 0.001 s; (E) ω0 = 600 MHz,
ω1 = 500 Hz, t = 0.0005 s; (F) ω0 = 1000 MHz, ω1 = 250 Hz, t = 0.001 s. All the pulses are on-resonance, i.e., ωp = ω0 = ωref. The blue and orange circles
denote the starting and end spin-state, respectively. A π x-pulse rotates +z-magnetization to the −y-direction.
2

Figure 7. Rotating-frame on-resonance pulses. On-resonance (A) π x-pulse (φp = 0, ω0 = ωref = ωp, ω1 = 1000 Hz, tp = 0.00025 s) rotates initial state |0,
2
π
0⟩, (B) π y-pulse (φp = π , ω0 = ωref = ωp, ω1 = 1000 Hz, tp = 0.0005 s) rotates initial state 2 , 0 , and (C) π x-pulse (φp = 0, ω0 = ωref = ωp, ω1 = 1000 Hz,
2 2
π 3π
tp = 0.00025 s) rotates initial state 2 , 2
. The initial and final states are denoted by red and orange arrows, respectively, and the rotation trajectory is
denoted by the black solid line.

Larmor frequency (offset = 0 Hz), precession about the z-axis is
effectively absent. Typically, RF-pulses are applied along the x-,
y-, −x-, and −y-directions. These correspond to pulse phases of
0, π , π, and 3π , respectively.
2 2
The program on-resonance-RF.py calculates the trajectory of
the spin in the rotating frame, in the presence of an on-resonance
RF-pulse, by taking as user input polar coordinates of initial spin-
state, amplitude of the pulse in Hz, and pulse duration. It rotates
the initial spin-state and outputs the final state on the terminal
and the trajectory of rotation graphically (Figure 7; eqs S8, S9,
and S10; Figure S9). An on-resonance π x-pulse rotates a spin-
2
state initially along the +z-direction to point along the −y-
direction (Figure 7A) or a spin-state initially along the −y-
direction to point along the −z-direction (Figure 7C) whereas
an on-resonance π y-pulse rotates a spin-state initially along the
+x-direction to point along the −x-direction (Figure 7B).
The take home message: Students should note the trajectories
of the spin in the laboratory frame (Figure 6, solid gray lines) and
the rotating frame (Figure 7, solid black lines). Students should
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also verify that, in the rotating frame, in the presence of an on-
resonance pulse, the magnitude of the Larmor frequency no
longer affects the trajectory, unlike in the laboratory frame.
Rotation in the Presence of Off-Resonance RF-Pulses in the
Rotating Frame
Off-resonance pulses are RF-pulses in which ωp and ωref are not
exactly equal to ω0 (see Rotating-Frame Approximation and RF-
Pulses). Unlike in the on-resonance case, this corresponds to a
reduced static magnetic field in the z-direction (B0′ ) (eq S4) and
a weak RF field away from the z-direction in the rotating frame.
The resultant magnetic field (Beff) which the spin experiences is
in a new direction, and the spin rotates about this “tilt axis”.
The magnitude of Beff is given by Beff = B0′ 2 + B12 and its
ω1 Ω0
direction by θp = tan−1 Ω0
, and φp, where B′0 = − γ
. The flip
angle for such an off-resonance pulse is = γBefftp. The
βoff
p
program off-resonance-RF.py takes as input the initial
orientation of the spin, ω0, ωref, ω1, φp, and tp. The program
calculates Ω0, assumes that ωp = ω0, and graphically outputs the
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Figure 8. Off-resonance effects in the rotating frame. An isolated spin 1/2 pointing in the z-direction (ω0 = 500 MHz) rotates when an off-resonance x-
pulse with ω1 = 1000 Hz is applied for 0.00025 s (corresponding to a π/2 flip angle in the laboratory frame) at an offset of (A) 0 Hz (corresponding to
an on-resonance x-pulse), (B) 1000 Hz, (C) 2000 Hz, and (D) −3000 Hz. The red and orange arrows indicate the initial and final orientations of the
spin. The gray arrow denotes the pulse-axis. The blue arrow denotes the tilt axis, and the black solid line denotes the trajectory of rotation.

Table 2. Comparison of Parameters for an On- and Off-

Resonance π x-pulse of the Same Duration tp = 0.00025 s for
2
■ CONCLUSION
To summarize, a set of 10 interactive Python programs are
an Isolated 1H with Varying Offset Frequencies presented here which can be used to visualize basic NMR
concepts accompanying in-depth theoretical derivations.
On-Resonance π x-Pulse in Off-Resonance π x-Pulse in Students can greatly benefit from these tools, before progressing
2 2
Parameters the Rotating Frame the Rotating Frame into more advanced concepts. The take home messages
Larmor frequency 500 500 following each section summarize the salient points and allow
(ω0) in MHz
students to test out important concepts themselves. Importantly,
these programs can be run without any prior programming
Offset (Ω0) in Hz 0 1000, 2000, −3000
knowledge, using free open source software on an operating
system of the user’s choice.

■
Beff in Hz

ASSOCIATED CONTENT
ω1 (Hz) and φp 1000 Hz and 0 1000 Hz and 0
(rad) *
sı Supporting Information

The Supporting Information is available at https://pubs.ac-

tp (s) 0.00025 0.00025
s.org/doi/10.1021/acs.jchemed.0c01008.
Flip angle (βp/βoff π Representative graphical and terminal outputs of Python
p )
in radians 2 programs described in this paper and relevant mathemat-
ical details (PDF)
initial and final orientations of the spin, the rotation trajectory, Python programs described in this paper and Jupyter
and the tilt axis (Figure 8 and Figure S10) along with a terminal/ notebook (ZIP)
notebook output. As the offset increases, the final spin-state ends Installation instructions for Python3, Numpy, Scipy, and
up further and further away from the −y-axis. Matplotlib (PDF)

The take home message: An on- and off-resonance pulse of
the same duration and amplitude rotate a spin by different
angles. Whereas an on-resonance π x-pulse rotates the spin,
2 Corresponding Author
initially pointing toward the +z-direction to the −y-direction
(Figure 8A), the off-resonance pulse, despite its larger flip angle
βoff
p , cannot bring the spin to point along the −y-direction in the
same time duration. This is because the axis of rotation is tilted
in the off-resonance case (Figure 8B−D). Students can calculate
the flip angles for an off-resonance pulse with varying offsets for
an isolated 1H (fixed ω0 and varying ωref); compare it to an on-
resonance π x-pulse of same duration, tp; and convince
2
themselves that this is indeed true (Table 2).
1679
■
AUTHOR INFORMATION
Ishita Sengupta − Department of Chemistry, IIT Bombay,
Mumbai 400076, India; orcid.org/0000-0002-2679-
6954; Email: ishita@chem.iitb.ac.in
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jchemed.0c01008
Notes
The author declares no competing financial interest.
https://doi.org/10.1021/acs.jchemed.0c01008
J. Chem. Educ. 2021, 98, 1673−1680
Journal of Chemical Education

■
pubs.acs.org/jchemeduc Article

ACKNOWLEDGMENTS
I.S. acknowledges financial support from IRCC, IIT Bombay,
and Science and Engineering Research Board, Government of
India (Grant SRG/2019/001988).

■ REFERENCES
(1) Levitt, M. H. Spin Dynamics: Basics of Nuclear Magnetic Resonance,
2nd ed.; John Wiley & Sons Ltd.: Hoboken, NJ, 2008.
(2) Keeler, J. Understanding NMR Spectroscopy, 2nd ed.; Wiley:
Chichester, U.K., 2010.
(3) Ernst, R.; Bodenhausen, G.; Wokaun, A. Principles of Nuclear
Magnetic Resonance in One and Two Dimensions; Clarendon Press:
Oxford, 1990.
(4) Lundberg, P. Educational NMR Software. J. Chem. Educ. 1997, 74
(12), 1489−1490.
(5) Bak, M.; Rasmussen, J. T.; Nielsen, N. C. SIMPSON: A General
Simulation Program for Solid-State NMR Spectroscopy. J. Magn. Reson.
2000, 147 (2), 296−330.
(6) Jerschow, A. MathNMR: Spin and Spatial Tensor Manipulations
in Mathematica. J. Magn. Reson. 2005, 176 (1), 7−14.
(7) Veshtort, M.; Griffin, R. G. SPINEVOLUTION: A Powerful Tool
for the Simulation of Solid and Liquid State NMR Experiments. J.
Magn. Reson. 2006, 178 (2), 248−282.
(8) Hogben, H. J.; Krzystyniak, M.; Charnock, G. T. P.; Hore, P. J.;
Kuprov, I. Spinach - A Software Library for Simulation of Spin
Dynamics in Large Spin Systems. J. Magn. Reson. 2011, 208 (2), 179−
194.
(9) Bengs, C.; Levitt, M. H. SpinDynamica: Symbolic and Numerical
Magnetic Resonance in a Mathematica Environment. Magn. Reson.
Chem. 2018, 56 (6), 374−414.
(10) Schwartz, L. J. A Step-by-Step Picture of Pulsed (Time-Domain)
NMR. J. Chem. Educ. 1988, 65 (9), 752−756.
(11) Macomber, R. S. A Primer on Fourier Transform NMR. J. Chem.
Educ. 1985, 62 (3), 213−214.
(12) Doscotch, M. A.; Evans, J. F.; Munson, E. J. Fourier Transform
Nuclear Magnetic Resonance Spectroscopy Experiment for Under-
graduate and Graduate Students. J. Chem. Educ. 1998, 75 (8), 1008−
1013.
(13) King, R. W.; Williams, K. R. The Fourier Transform in
Chemistry. J. Chem. Educ. 1989, 66 (10), A243−A248.
(14) Autschbach, J.; Le Guennic, B. Analyzing and Interpreting NMR
Spin − Spin Coupling Constants Using Molecular Orbital Calculations.
J. Chem. Educ. 2007, 84 (1), 156−171.
(15) Bryce, D. L.; Wasylishen, R. E. Ab Initio Calculations of NMR
Parameters for Diatomic Molecules An Exercise in Computational
Chemistry. J. Chem. Educ. 2001, 78 (1), 124−133.
(16) Johnson, C. S.; Moreland, C. G. The Calculation of NMR Spectra
for Many-Site Exchange Problems. J. Chem. Educ. 1973, 50 (7), 477−
483.
(17) Morris, K. F.; Erickson, L. E. NMR Determination of Internal
Rotation Rates and Rotational Energy Barriers. J. Chem. Educ. 1996, 73
(5), 471−473.
(18) Spiese, C. E. A Simplified Approach to Product Operator
Formalism. J. Chem. Educ. 2004, 81 (1), 134−137.
(19) de la Vega-Hernandez, K.; Antuch, M. The Heteronuclear Single-
Quantum Correlation (HSQC) Experiment: Vectors versus Product
Operators. J. Chem. Educ. 2015, 92, 482−487.
(20) Anderson-Wile, A. M. Introducing 2D NMR Spectroscopy to
Second-Year Undergraduate Chemistry Majors Using a Building-Up
Approach. J. Chem. Educ. 2016, 93, 699−703.
(21) Shankar, R. Principles of Quantum Mechanics; Springer: Boston,
MA, 1994.
(22) Bloch, F. Nuclear Induction. Phys. Rev. 1946, 70 (7−8), 460−
474.

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