The continued non-detection of WIMP and AXION elementary particles, which were prime candidates for dark matter, raises a fundamental question: Could water nanoclusters hold clues to understanding these cosmic enigmas? It is essential to recognize the predominant role of hydrogen and oxygen - the constituents of water - in our universe. Both are among the most abundant and chemically active. Intriguingly, water vapor plays a pivotal role during the early phases of star creation. In these regions, water acts as a significant oxygen reservoir, ensuring the effective cooling of the surrounding gas, which is a crucial process in star evolution [
8]. In fact, regions such as the Orion nebula are known to generate immense amounts of water daily, much more than the volume of Earth's oceans [
9]. Moreover, the discovery of massive reservoirs of water, associated with high-redshift quasars, twelve or more billion light-years from Earth, underscores the widespread presence of water in the universe [
10]. Such quasars, housing astounding masses of water vapor, are indicative of water's abundance even in remote cosmic locales. Furthermore, recent studies suggest that during the universe's infancy - the initial billions of years post Big Bang - water could have been quite widespread [
11]. Closer to home, stable water nanoclusters arise in the atmosphere because of hydrogen bonding between water molecules [
12]. A plausible mechanism for the formation of these nanoclusters in the cosmos is cosmic-ray-induced direct ejection from amorphous ice covering cosmic dust grains, as observed under laboratory conditions [
2]. These grains, which are prevalent in interstellar clouds, owe their existence to supernovae explosions [
13]. The cosmic-ray-induced ionization of H
2 molecules adsorbed on amorphous water-ice, namely, H
2+ + nH
2O + grain → H
3O
+(H
2O)
n-1↑ + grain, is another proposed scenario for the ejection of protonated water nanoclusters to interstellar space [
14]. These ionized water nanoclusters, owing to their oscillating electric dipole moments, are linked to the observed THz emissions from water vapor under intense UV radiation [
15] and thus should be stable under similar cosmic radiation. Interestingly, H
3O
+(H
2O)
20 or its equivalent protonated form, (H
2O)
21H
+ is notably stable under vacuum conditions. This “magic-number” structure can be visualized as a hydronium ion, H
3O
+ encased by a pentagonal dodecahedral assembly of twenty water molecules (
Figure 1d). The stability of this unique structure may have cosmic implications, as suggested by the recent observation of interstellar hydronium [
16]. Spectroscopic identification of larger protonated cosmic water nanoclusters is a challenge, but crucial for confirming their presence and understanding their possible role in cosmic phenomena.
Figure 1 illustrates the ground-state molecular-orbital energies, wavefunctions, and vibrational modes of the protonated pentagonal dodecahedral water cluster, (H
2O)
21H
+. These results were obtained using the SCF-Xα-Scattered-Wave density-functional method, a collaborative development by the author [
17]. Molecular dynamics simulations confirm the stability of the cluster at temperatures exceeding 100°C, with minimal changes. Similar calculations were performed for the neutral pentagonal dodecahedral water cluster, (H
2O)
20, and its arrays, revealing THz vibrational modes, as depicted in
Figure 2 and
Figure 3.
Figure 2 and
Figure 3 exhibit qualitative resemblance to
Figure 1c,d but show a gradual decrease in the vibrational frequency cutoff as the cluster size increases. This trend aligns with experimental observations of THz radiation emission from water vapor nanoclusters [
15], as depicted in
Figure 4. The shift in THz emission peaks towards lower frequencies and intensities, corresponding to larger clusters, occurs with decreasing water vapor ejection pressure in the vacuum chamber where the radiation was measured. This observation suggests a decrease in THz emission cutoff frequencies and intensities as water nanoclusters of increasing sizes are ejected from ice-coated cosmic dust.
Common characteristics among all these water clusters include: (1) lowest unoccupied (LUMO) energy levels, akin to those in
Figure 1a, corresponding to diffuse Rydberg cluster "surface" molecular-orbital wavefunctions depicted in
Figure 1b as "S," "P," "D," and "F"-like orbitals and (2) bands of vibrational modes ranging from 0.5 to 6 THz (
Figure 1,
Figure 2 and
Figure 3) due to O-O-O "squashing" or "bending" and "twisting" motions between adjacent hydrogen bonds. The vectors in
Figure 1,
Figure 2 and
Figure 3 represent the directions and relative amplitudes of the lowest THz-frequency modes associated with the O-O-O "bending" (or "squashing") motions of the water-cluster "surface" oxygen atoms. Observations of surface O-O-O bending vibrations in this energy range have been performed under laboratory conditions [
18]. Furthermore, ultraviolet excitation of an electron from thehighest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO), as shown in
Figure 1a, can place the electron into the Rydberg "S"-like cluster molecular orbital illustrated in
Figure 1b. Occupancy of this orbital results in a bound state, even when an additional electron is introduced, leading to the formation of a "hydrated electron" [
19]. In contrast, a water monomer or dimer exhibits virtually no electron affinity. Therefore, in space, particularly within dense interstellar clouds, a water nanocluster, (H
2O)
21H
+ or H
3O
+(H
2O)
20, ejected from amorphous water-ice-coated cosmic dust, is likely to capture an electron, leading to electrically neutral water nanoclusters, as shown in
Figure 2.