3.1. Helium (2He)
Helium is, after hydrogen, the second lightest and second most abundant element in the universe. Helium has similar behavioral properties to that of an ideal gas and exists as a monoatomic substance. It fulfils the Universal Gas Law with a good approximation. Completely nonreactive, it does not form any known chemical compounds. However, new materials with helium incorporated into the fullerenes were synthesized and spectroscopically investigated [
28]. Helium in the Earth’s atmosphere is relatively rare, ~5.2 ppm by volume. There are nine isotopes of helium from
2He up to
10He, but only two of them are stable:
3He (
I = 1/2) and
4He (
I = 0) [
29]. The isotopic abundance of the first isotope in the Earth’s atmosphere is 1.37 parts per million (0.000137%); however, only this nuclide can be applied in NMR measurements.
In the perspective of theoretical physics, He is subject to the laws of quantum statistics;
4He are bosons but
3He are fermions. Liquid helium exhibits the strongest quantum effects. Both isotopes play an important role in cryogenic applications as a source of extremely low temperatures. A rare isotope of helium—
3He, is used as a refrigerator to achieve temperatures of the order of 0.2 to 0.3 K and in mixtures with
4He to reach temperatures as low as a few thousands of a kelvin. The boiling points of helium isotopic forms (4.23 K, 3.1905 K for
4He and
3He, respectively) are lower than those of any other substance. Commercially, helium-3 is manufactured through the nuclear decay of tritium, a radioactive isotope of hydrogen. The most effective commercial source of helium-3 is the nuclear weapon utilization program in the U.S. [
30].
Precise knowledge of the helium-3 NMM is of prime importance because a small nucleus (2 protons and 1 neutron) can be good to test the summation of neutron and proton magnetic moments. This outstanding nucleus has its mirror analog in the tritium nucleus. The nuclear spin of helium-3 (triton) was determined from the intensity alternation in the band spectrum of the helium dimer [
31]; the sign of the
3He nuclear magnetic moment is opposite to that of the proton [
32]. Over the last seventy years, several attempts have been made to precisely determine the
3He nuclear magnetic moment. The first attempt was made by Anderson and Novick in 1949 [
33] in an NMR experiment using helium and water H
2O, where the g-factor of
3He was roughly established as 0.763 of a proton.
All systems under examination, used to establish μ(
3He), are listed in
Table 1 [
34,
35,
36,
37,
38,
39,
40,
41,
42] along with the appropriate diamagnetic corrections and magnetic moments and will be discussed shortly.
Anderson attempted the precise measurements of μ(
3He) in a gaseous mixture of
3He/H
2/O
2 (1/0.37/1 proportion and pressure of 24 atm) and received the result of 0.7617866(13) for the ratio of the frequencies ν(
3He)/ν(
1H) [
34]. However, the presence of large amounts of paramagnetic oxygen (which can cause a change of local magnetic field) reduced the validity of this experiment, despite good agreement with the next achievements. This result was upgraded to an accuracy of 0.1 ppm by Williams and Hughes [
35]—0.76178685. Progress has essentially been achieved in this area because of the efforts Neronov et al. in a series of papers [
36,
41,
42].
Discussion regarding the older results of gas phase experiments in the
3He/H
2/HD/D
2/O
2 mixtures can be omitted as the presence of large amounts of paramagnetic oxygen ingredients can falsify the final results. Very precise measurements lead to a ratio of
3He/
1H NMR spin precession frequencies 0.761786594(2) in the
3He/H
2 mixture [
41] and to a
3H
3/
2H ratio of 4.962582261(4) in the
3He/D
2 mixture [
42]. The final results of the NMM mentioned above (see
Table 1) were corrected by factors that came from shielding parameters of helium-3 σ
0 = 59.96743(10) ppm [
43] and from protons in H
2 (26.293(5) ppm) and deuterons in D
2 molecules (26.288(3) ppm)) [
17]. For recalculation of the original results, we have used the best known shielding corrections and magnetic moments of proton [
44] and deuteron [
11] (see
Table 1).
More reliable experiments will be those carried out by Flowers, Petley, and Richards [
38] in pure helium-3 samples against the proton signal in liquid water. The frequency of optically pumped
3He nuclei and that of protons in water H
2O were measured in an accurately spherical sample cell in the same magnetic field of 0.1 T and 25 °C. The interchange of sample
3He and water was carefully computer controlled. Several corrections of temperature, magnetic field homogeneity, shape correction, and other things were involved. These accurate measurements and new corrections for shielding in water samples (25.691(11) ppm [
11]) and that of
3He lead to a final result of μ(
3He) = 2.127625308(25) μ
N. The last value was included in the latest collections of fundamental physics constants, namely those recommended by Stone in the “Table of recommended nuclear magnetic dipole moments” published under the auspices of the INDC (International Nuclear Data Committee, November 2019 [
45].
Another approach to these studies was made by Jackowski et al. [
40] from experiments that related the resonance frequency of the
3He nucleus to the resonance frequency of the
1H nucleus in neat tetramethylsilane (TMS). For the first time, the pressure dependence of
3He chemical shifts was observed in the gaseous phase and the radiofrequency for the isolated helium atom was given. The shielding correction in liquid TMS was then applied as σ (
1H, TMS) = 32.815(5) ppm [
17], and in liquid cyclohexane-d
6 as σ (
2H, (CD
2)
6) = 31.834 ppm [
46].
For purpose of this work, new experiments in gaseous H
2/
3He mixes were performed. Namely, three different mixtures were examine—
3He/H
2 in CO
2, N
2O, and CF
4 as buffer gases to measure the frequency ratio of
3He/
1H in the zero-pressure limit (see
Figure 1). To fulfill Equation (8) the minor components in gas mixtures (
3He-H
2) were maintained at small concentrations less than 5 × 10
−3mol/L. CO
2, N
2O, and CF
4 buffer gases were used in much excess. All data points are from single measurements of one dimensional NMR spectra. The density function plots were analyzed according to the Equation (7). Only in this case are the diamagnetic corrections adequate in the theoretical results for molecules in a vacuum—for the isolated He atom and H
2 molecules at a given temperature of 300 K.
The extrapolated average frequencies are as follows: υ(
1H) = 500.6089872(17) and υ(
3He) = 381.3572158(5) MHz. The appropriate shielding correction was applied to establish the final result for bare nuclei. All calculated helium-3 magnetic moments from experiments with different buffers were from −2.127625286(15) up to −2.127625333(16) μ
N, in agreement with the previously reported results. At this high precision, the calculations for all component errors are important. However, the main source of error originates from the proton shielding correction factor in the H
2 isolated molecule [
17].
In summary, we can ascertain that the helium-3 dipole moment belongs to the more precise values established for any nucleus in the periodic table apart from proton and deuteron. It is important that helium atoms can be used in different gaseous mixtures for comparative NMMs measurements of other nuclei. All results from the experimental observations up to now are schematically shown in
Figure 2.
The tendency for the stable NMM results around the value 2.1276263μN has been accomplished over time and is clearly visible. Good agreement between the old result of Anderson (1949) and more recent ones (2008, 2012, and 2020) can be of accidental origin when errors and approximations cancel each other out. Only the extrapolated parameters and shielding corrections for isolated atoms or molecules are methodologically correct. The above results show that NMR spectroscopy has reached its limit for further improving the results using the standard NMR method in this case. The other advanced physical methods could lead to radical progress in the future.
3.2. Neon (10Ne)
Neon is the fifth most abundant element in the universe (fourth according to the Jefferson Laboratory). It is present in the Earth’s atmosphere at 0.0018% by volume, and is lighter than air. Liquefied is an important cryogenic refrigerant. It is commercially available from the fractional distillation of liquid air. Interestingly, neon was the first element recognized as a mixture of three stable isotopes. It consists of three stable isotopes:
20Ne (90.48%),
21Ne (0.27%), and
22Ne (9.25%) [
29].
22Ne is used for the production of radioisotope
22Na in medical treatment and
20Ne is a precursor of
18F used in the radiopharmaceutical industry. Only Ne-21 (
I = 3/2), apart from maser building, can be used to study the NMR resonance. Unfortunately, the nucleus—
21Ne possesses quite a large quadrupole moment Q = 0.10155(75) barn [
45] but in a very symmetrical environment, the resonance lines are expected to be not too wide. Neon forms no chemical compounds.
21Ne NMM was measured for the first time by LaTourette et al. against the deuterium signal of D
2 [
47] in an ABMR experiment. The original value of the NMM was −0.661758(5), and this was recalculated using the new magnetic shielding coefficient μ(
21Ne) = −0.6617895 μ
N. This value was recently measured by NMR spectroscopy performed in the gas state on neon gas at the natural abundance: −0.6617774(10) [
48]. The pressure dependence of NMR frequencies was determined in the density range 0.13–2.90 mol/L. This function shows a strictly linear dependence. The
21Ne frequency results were compared with those for the
1H frequency of the residual signal of benzene-d
6 used as a “lock” reference.
We cannot use helium-3 to measure the NMM of neon-21 because its low resonance frequency means that neon measurements must be made on a low band probe where the frequency of helium-3 cannot be achieved. The second reason for this not being possible was the fact that large glass ampoules with 8 mm o.d. not suited to the helium measurement probe had to be used. Instead of this, we chose the residual signal of
1H and
2H(D) resonance frequencies as reference nuclei of the lock system (see
Table 2). The main source of the shielding factor correction is for the neon isolated atom. Its magnetic shielding can certainly be taken from chemical quantum calculations. They are in the range of 561.3–556.83 [
48]. We chose the recently calculated result of 557.1123 ppm by the four-component relativistic method [
49]. Finally, it can be seen that both experimental techniques, ABMR and gas phase NMR, lead to practically the same result, which only varies by 0.016% (see
Table 2).
The noble-gas polarization technique of spin exchange with laser optically pumped Rb allows several noble gases to be polarized simultaneously, among them helium-3 and neon-21 and the free resonance frequency to be observed [
50]. A rather large error in frequencies gave the NMM of neon-21 with limited precision.
The theoretical physical attempts to calculate μ(
21Ne) provided several, slightly different values: 0.660, 0.774, 0.824, 0.741, and 0.688 in nuclear magnetons, depending on the method used [
51]. Using the example of neon, we are able to discuss the NMM measurements of short-lived nuclei from the fast-beam collinear laser spectroscopy method [
52]. In addition to the NMMs, there are other important physical properties that describe the form of particular nuclei: quadrupole electric moments (in barn, 1b = 10
−28 m
2) and mean square charge radii. Both electromagnetic moments for different neon isotopes [
53], among them unstable nuclei, are shown in
Table 3.
3.3. Argon (18Ar)
After nitrogen and oxygen, argon gas is the third most abundant component in dehydrated atmospheric air. Argon has 24 known isotopes from
30Ar up to
53Ar but only three of them are stable:
36Ar (0.3365(30)%),
38Ar (0.0632(5)%), and
40Ar (99.6003(30)%) [
29]. Unfortunately, none of them are magnetically active. Three other isotopes are relatively long-lived:
39Ar (with a half-life of 269 years),
42Ar (32.9 years), and
37Ar (35.04 days). Almost all argon on Earth comes from the short living
40K (0.012% of natural potassium) isotope in a series of nuclear transformations. Isotopes
37Ar and
39Ar can potentially be used in NMR experiments. The second one is an especially promising experimental object.
The content of
39Ar in natural argon is only 8 × 10
−16 g/g, and it comes from the cosmogenic reaction from
40Ar in the upper atmosphere. These radionuclide form in the atmosphere through the nuclear reaction
40Ar(n,2n)
39Ar and decay by beta emission to
39K with a half-life of 269 years [
54]. We propose using this isotope in the NMR exploration of argon chemical shifts in the future, while carefully considering radioactive material. The nuclear magnetic properties are known:
I = 7/2 and μ(
39Ar) = −1.588(15) [
55].
It is possible to predict other NMR quantities—chemical shift range from −110 up to 0.0 ppm, relative resonance frequency Ξ = 8.1222%, line width ~4 Hz and receptivity relative to
1H ~1 × 10
−16 [
56]. Argon magnetic properties were very rarely a research subject in the literature. For this reason, the ab initio calculations of intermolecular interactions in ArAr, ArNaH, and ArNe systems carried out by Jameson et al. [
57] are of prime importance in this field. A few basic properties of argon isotopes are shown in
Table 4. The magnetic and quadrupole moments were measured by NMR of beam polarized nuclei with β asymmetry detection (β-NMR), collinear fast beam laser spectroscopy with β detection (CFBLS/ β-NMR), and optical pumping with radiative detection (OP/RD) [
58].
3.4. Krypton (36Kr)
The Earth’s atmosphere contains about 1.14 ppm of krypton by volume and 10 ppt in the Earth’s crust. It is used commercially and is easily separated from liquid air by fractional distillation. Naturally occurring krypton is composed of five stable isotopes:
80Kr (2.286%),
82Kr (11.593%),
83Kr (11.500%),
84Kr (56.987%),
86Kr (17.279%), and
87Kr (0.355%) with a very long half-life of 9.2 × 10
21 years. Additionally, about 30 unstable isotopes and isomers are known among them
85Kr with a long half-life of 10.776 (3) years [
59]. This last isotope is produced in nuclear reactors and power plants. In the atmosphere, it is monitored as a good source of information regarding the consumption of nuclear material in a given area. Krypton can form nothing but a few simple compounds with other atoms under extreme conditions: KrF
2, KrF, KrXe, HKrCN, HKrC≡CH, and Kr(H
2)
4 [
60]. Only krypton difluoride, a strong oxidizer, has been synthesized in gram quantities using several methods.
83Kr as the only naturally occurring and magnetically active krypton nucleus with the spin number
I = 9/2 was used in common NMR investigations in the gaseous state and in solutions. It deviates slightly from the spherical symmetry and should be described as a deformed nucleus that manifests itself with a relatively high electric quadrupole moment Q = +0.259 × 10
−28 m
2 (0.259 barn) [
45]. The nucleus
83Kr has 36 protons and 47 neutrons and is notable for its one high spin orbital, 1g
9/2.
For the first time, the μ(
83Kr) was measured using the ABMR method [
61], but with rather limited precision. Afterward, NMR investigations gave more accurate results: μ(
83Kr) = −0.9707295μ
N [
62] and μ(
83Kr) = −0.967221 μ
N [
63]. The
3He and
83Kr NMR frequencies were only recently measured using an advanced technology pulse FT spectrometer in
3He/Kr gaseous mixtures at different densities [
64]. Selected krypton spectra are shown in
Figure 3. The frequency dependences were analyzed according to Equation (8). The density shift was measured per concentration unit as σ
1(Kr,Kr) = −3259.1(300) ppm ml mol
−1. The difference between low and high pressures attains a few ppm and cannot be ignored if shielding corrections are to be properly included. The final result completed against the helium-3 moment is −0.9707297(32) μ
N and remains in excellent agreement with the previous result of Brinkmann et al. [
63].
In addition to the magnetic moment for the
I = 9/2 ground state
83Kr nucleus, the magnetic moment of the metastable krypton
83mKr (half-life 1.83 h) nucleus was measured by collinear fast-beam laser spectroscopy in arrangement with sensitive collisional ionization detection [
65]. The short lived isomeric state
83mKr (
I = 1/2
−) excited at 41.55 keV can be generated from the radioactive
83Rb source (T
1/2 = 86.2 d). The difference between the NMM in the ground and the first excited state is valuable and equals 1.562 μ
N (see
Table 5).
3.5. Xenon (54Xe)
At standard conditions (temperature and pressure) gaseous xenon has a density of 5.761 kg/m
3. Xenon can be liquefied at −111.7 °C (161.4K). Surprisingly, in the liquid state xenon possesses high polarizability and can be a good solvent for many hydrocarbons and even water. It is found in the Earth’s atmosphere at a concentration of 8.7 ppb by volume. Generally, it is unreactive but can form many stable compounds, mainly with strong electronegative elements, such as fluorine and oxygen: XeF
2, XeF
4, XeOF
2, XeF
6, XeO
4, H
6XeO
6, XePtF
6, and many ionic species in water solutions [
66]. NMR spectroscopy of xenon is, therefore, an interesting and still progressive field of spectroscopy [
67]. Xenon is obtained commercially by extraction from liquid air.
A naturally occurring element, it consists of seven stable isotopes:
126Xe (0.089%),
128Xe (1.910%),
129Xe (26.401%),
130Xe (4.071%),
131Xe (21.232%),
132Xe (26.909%), and
134Xe (10.436%). A few other isotopes are long lived:
124Xe (0.095%, 1.8x1022y),
125Xe (16.9 h),
127Xe (36.345 d) and
133Xe (5.247 d),
135Xe (9.14h), and
136Xe (8.857%, 2.165 × 10
21 y) [
29]. In the magnetic resonance method, two nuclides of natural abundance can be utilized:
129Xe (with 75 neutrons) with the spin number
I = 1/2
- and
131Xe (with 77 neutrons) with
I = 3/2
+.
Kopfermann et al. determined from the hfs (hyperfine structure) measurements that the former has a spin of 1/2 and the latter a spin of 3/2 [
68]. The receptivity of the
129Xe nuclei is 5.72 × 10
−3 of that of a proton and encompasses a large spectral range of 5800 ppm due to its extreme sensitivity to the different chemical environments. Interestingly, the lower sensitivity nucleus
131Xe, which is quadrupolar, can show additional signals in the gas phase when gas-solid glass ampoule collisions take place. This behavior is depicted in
Figure 4a along with the analogous signal of
129Xe, which has
I = 1/2 and no quadrupole moment (
Figure 4b). Gas-phase
131Xe atoms exhibiting nuclear quadrupole interactions with the surface of the glass samples were observed earlier and explained by the model of atoms absorbed on surfaces (see for example [
69]) and high magnetic field strength [
70].
One of the first measurements of the NMM was performed by Proctor and Yu [
71] for a number of nuclei, including for
129Xe. Brun et al. [
72] measured both xenon active isotopes a few years ago with much more precision in pure gas at approximately 50 atm. against that of protons in water containing 0.1 M MnSO
4 as the relaxation reagent. It was seen that the chemical shift/frequency of xenon resonances were strongly dependent on the gas density, which reinforced the measurements in the series samples of different pressures.
Brinkmann [
73] measured the NMM of xenon isotopes taking the deuteron nucleus in heavy water, with small amounts of FeCl
3 as a relaxation agent, as a reference standard. However, the use of paramagnetic substances can modify the final result to the same extent. The next attempt to better establish the
129Xe magnetic moment took place when Pfeffer and Lutz [
74] made their experiments in xenon dopped oxygen to shorten the rather long relaxation times. They received an impressive precision result of 0.2766027337(30). The usage of oxygen ingredients can also slightly mangle the final number. All the above results of measurements are shown in
Table 6.
The author’s latest work on this topic was published recently on experiments free of methodological limitations [
75]. Small amounts of
3He or
3He/Xe mixture (≤ 3.0 × 10
−3 mol/L, pressure ~80 mmHg) as the solutes and pure Xe or SF
6 and CO
2 gases were taken as the buffers. They were analyzed in
3He and
129Xe NMR spectra at the external field, B
0 = 12.7586 T. In each case, the resonance frequencies (ν
He and ν
129,131Xe) were linearly dependent on the total density of the xenon gas. Extrapolation to the zero-density limit allowed these frequencies to be evaluated as free from intermolecular interactions. Combining these values with the recommended σ (
129/131Xe) and σ (
3He) nuclear magnetic shielding constants led to the following final results: μ(
129Xe) = −0.7779607(158) μ
N and μ(
131Xe) = +0.6918451(70) μ
N.
In our opinion, these are the best results known up to now for both xenon magnetic moments. A direct and precise determination of
3He/
129Xe was performed recently in a comagnetometer setup under an ultralow ambient magnetic field (0.4 < μ
T) [
76]. From the ratio of γ(He)/γ(Xe), the magnetic moment of
129Xe was obtained as −0.77796029(2) μ
N, which is in very good agreement with our former result. The ratio of two different xenon magnetic moments can be given as 1.1244724, which is in accord with our measured ratio 1.12447237.
3.6. Radon (86Rn)
Radon is a naturally-occurring chemical element as an α,β-radioactive gas. It is produced as an intermediate step in the radioactive decay chain of radium (T1/2 ~1600 years). As it is a final radionuclide of the decay chain of thorium and uranium (two of the most common radioactive elements on Earth, which have three isotopes with very long half-lives), it is seen in many places as it is a continually generated natural substance. It is nonreactive chemically and, therefore, does not form chemical compounds. Radon concentrations in the atmosphere are too low to be measured by standard chemical methods. However, a few reports on the existence of compounds involving oxygen and fluorine bound to radon have occurred.
At present, there are 35 known isotopes of radon, and all are radioactive [
29]. The most stable is the
222Ra isotope with a half-life of 3.823 days. Two other isotopes occur in nature:
219R and
220Ra with a half-life of less than 1 min. A few other isotopes exist in trace quantities as decay products or as intermediates in the decay chain of different heavier isotopes. The most favorable conditions of NMR measurements belong to
211Rn with a half-life 14.6 h and spin number 1/2. The nuclear magnetic moment of this isotope was established as μ(
211Rn) = 0.601(7)μ
N. The nuclear moments—both magnetic dipole and electric quadrupole—belong to odd mass numbers of radon. They were established formerly by the spin-exchange optical pumping method [
77]. Selected nuclear properties of radon isotopes are shown in
Table 7.
3.8. Theoretical Calculations of NMMs
At the end of our considerations, it is necessary to mention the pure theoretical achievements in the field of nuclear magnetic moment calculations. The experimentally measured moments are “highly sensitive to the underlying structure of atomic nuclei and, therefore, serve as a stringent test of nuclear models” [
6]. In the past decades, the different theories of nuclear structure were developed starting from the single particle shell model up to the covariant DFT (Density Functional Theory) model, incorporating relativistic effects with several additional corrections e.g., one-pion exchange-current.
Several semi-empirical calculated results for the helium-3 nucleus were discussed in factor g
I terms: g
I(
3He) = −3.826 (Schmidt line), g
I(
3He) = −4.255 (EV,FT) and g
I(
3He) = −4.220 (full-scale shell) compared with the experimental value of g
I(
3He) = −4.2552506(1) [
79]. On the other hand, the best result in the quark model gave the values g
I(
3He) = −4.009828, g
I(
3He) = −3.826084 in the shell model, g
I(
3He) = −4.5810 in the QCD (Quantum Chromodynamics) model [
80] and g
I(
3He) = −4.16 in the effective field theory (EFT) of short range interactions [
81].
Even in the case of helium, a very simple nucleus, the precision and accuracy of the theoretical predictions is far from those of experimental achievements. This statement is valid for all nuclei in the periodic table, and for all nuclei of remaining noble gases. Nuclear theories have a limited ability to make precise calculations. For readers interested in these problems, the following papers are recommended: for
21Ne calculations [
82], and for xenon nuclei [
79].