Singly charged heavy ions observed in the magnetosphere, such as atomic N⁺ and O⁺, and molecular N 2 + , NO⁺, and O 2 + ions, are sourced from the Earth’s ionosphere, and transported outward through the process of ionospheric escape. One of the main pathways of ionospheric loss is the polar wind, an ambipolar flow of plasma from the high-latitude ionosphere to the low pressure magnetosphere. This outflow (Axford and Hines, 1961; Shelley et al., 1972; Yau et al., 1991; Maggiolo et al., 2006; Schunk and Nagy, 2009; Kronberg et al., 2014; Ilie and Liemohn, 2016; Glocer et al., 2018; Lin et al., 2020) provides a pathway for atmospheric migration and escape at a rate that generally depends on solar extreme ultraviolet (EUV) photon flux striking the upper atmosphere, as well the electromagnetic driving from the solar wind. Therefore, heavy ions of ionospheric origin can be directed and further circulated into different regions of the magnetosphere: either on closed magnetic field lines (plasma sheet) where ions can potentially be returned to the ionosphere, or on open magnetic field lines (lobe region) directly connected to the interplanetary magnetic field where ions are lost to space (Christon et al., 1994; Haaland et al., 2012a; Haaland et al., 2012b; Ilie et al., 2013; Yamauchi, 2019). Figure 1 shows an illustration of polar wind ion species, which could be created by the photoionization with the neutral atmosphere (and other ion-neutral-electron chemical reactions) and accelerated along magnetic field lines.

The dynamics leading to the ionospheric outflow of O⁺ ions, and the impact on the evolution of the Earth’s magnetosphere-ionosphere system have been the subject of numerous studies (e.g., Schunk and Raitt, 1980; Mukai et al., 1994; Schunk and Sojka, 1997; Seki et al., 1998; Daglis et al., 1999; Moore et al., 1999; Winglee et al., 2002; Nosé et al., 2005; Barakat and Schunk, 2006; Yau et al., 2007; Glocer et al., 2009; Garcia et al., 2010; Glocer et al., 2012; Ilie et al., 2013; Ilie et al., 2015; Lin et al., 2020). In contrast, the transport and energization of molecular ions, in addition to that of N⁺ and O⁺ ions, have received less attention, most likely due to the scarcity of measurements.

It is known that N 2 + , NO⁺, and O 2 + ions are the major ion populations in the ionospheric E and F layers, and primarily created through photoionization and ion-neutral-electron chemical reactions. These molecular ions maintain low energies due to their large masses and short dissociative recombination lifetimes with electrons, as they quickly form a pair of neutral atoms. In the F layer, the reaction rates of dissociative recombination of O 2 + and NO⁺ are approximately 10^–7 cm⁻³ s⁻¹, while those of the charge exchange reactions to remove O⁺ are approximately 10⁻¹¹ cm⁻³ s⁻¹. Despite the fact that the abundance of molecular ions decreases significantly in the F2 layer, multiple missions reported their presence throughout the magnetosphere-ionosphere system (Taylor, 1974; Grebowsky et al., 1983; Craven et al., 1985; Klecker et al., 1986; Yau et al., 1993; Christon et al., 1994; Wilson and Craven, 1999; Lennartsson et al., 2000; Seki et al., 2019; Christon et al., 2020).

Figure 2 shows space missions that reported observations of molecular ions, starting from the early Sputnik III spacecraft to the Arase (ERG) mission, spanning from few hundreds km altitude to hundreds of Earth radii across several solar cycles. In this letter, we review the observational record of molecular ions from the Earth’s terrestrial high latitude ionosphere to the magnetosphere. These observations provide context to understand the energization of molecular ions, as well as to help interpret plasma observations from current and past space missions.

Molecular N 2 + ions were first observed in the topside ionosphere by the Bennett-type radio frequency (RF) quadrupole mass spectrometer on board of the Soviet Sputnik III satellite (Nauk and Doklady, 1961). Launched on May 15, 1958, Sputnik III satellite aimed to observe the ionic compositions in the topside ionosphere, and its altitude range covered from 217 to 1864 km with 65.18° orbital inclination. Figure 3 presents the first in situ observations of N⁺ and N 2 + densities as a function of altitude. These measurements from Sputnik III show that the density of N 2 + is higher than that of N⁺ at altitudes below 300 km, reaching a peak density of 9.8 × 10³ cm⁻³ around 250 km altitude (Istomin, 1966). The reason for the fast decrease in N 2 + density at higher altitudes is that in the F2 layer, N 2 + undergoes fast recombination reactions with electrons to form a pair of neutral atoms, and charge exchanges quickly with most of the other neutral species. Thus, the concentration of N 2 + rapidly decreases above 300 km altitude. On the other hand, N⁺ is produced via N 2 + dissociation and its concentration increases rapidly by 2–3 orders of magnitude as the altitude increases.

Previous observational data sets (Taylor et al., 1968; Johnson and Gerardo, 1972; Taylor, 1973) indicated that the abundances of molecular ions rapidly decreased due to short dissociative recombination lifetime, and therefore molecular ions were only occasionally observed. Thus, it has been concluded that the density of molecular ions in the topsides ionosphere is negligible. However, the Polar Orbiting Geophysical Observatory (OGO 6) mission launched on June 5, 1969, one of the first U.S. led large observatory to study the dynamics of high-altitude atmospheric parameters (Jackson and Vette, 1975), was the first to report observations of the high latitude trough (HLT), a prominent feature associated with the presence of molecular ions in the topside ionosphere (600–1,000 km). This HLT is a narrow (6°–10° latitude) region where the concentration of atomic H⁺, He⁺, O⁺ and N⁺ were observed to decrease by a factor of 3 or more, while molecular N 2 + , NO⁺, and O 2 + ion densities presented abrupt enhancements.

Although the inclination of the OGO 6 orbit was 82° north, due to the tilt of the dipole axis, OGO 6 covered a wide range of latitudes (Taylor, 1971), and the data coverage ranges from ∼ 413 km to ∼ 1077 km altitude. These unexpectedly abrupt and pronounced distributions of molecular ions were measured by the Bennett-type radio frequency ion mass spectrometer (Taylor, 1973) onboard OGO 6, showing enhancements in the density of NO⁺ that reached 10³ cm⁻³ at 1,000 km altitude near 70°–80° latitude, both in the northern and southern hemisphere, during the modest storm of June 20, 1970 (Max Kp = 4; Min Dst = −54 nT).

These large gradients in the abundances of molecular ions observed in the HLTs were later explained by the enhancement of soft electron precipitation associated with the polar cap region and the rapid loss of O⁺ due to the strong electric convection field (Taylor et al., 1975; Grebowsky et al., 1976; Grebowsky et al., 1983). On March 10, 1970, 1 day after the intense geomagnetic storm of March 8, 1970 (Max Kp = 9; Min Dst = -285 nT), the HLT was observed at altitudes between 700–800 km, and ∼ 65.8° latitude in the northern hemisphere and ∼ -65.2° latitude in the southern hemisphere. Figure 4 shows the measurements of O⁺, H⁺ and NO⁺ densities from OGO 6 satellite versus latitudes, extracted during the recovery phase of March 8, 1970 geomagnetic storm. It can be seen that in both HLT regions (with ∼ 5° latitude range, highlighted as light orange), ∼ 50% of both O⁺ and H⁺ densities are depleted at a time when NO⁺ ions density increased about a factor of 8, while the peak value of NO⁺ concentration was up to 20 cm⁻³ at ∼ 700 km altitude. These observations suggest that the rapid loss of O⁺ in the HLTs could contribute to the source of NO⁺ ions through the reactions of O⁺ ions with the neutral atmosphere, O⁺ + N₂ → N + NO⁺ and possibly O⁺ + O₂ → O 2 + + O . Note that the OGO 6 also had ability to distinguish the increasing ion densities of N 2 + and O 2 + , but were not shown here due to clarity of the figure (Taylor et al., 1975). Grebowsky et al. (1983) further examined the average invariant latitude-magnetic local time (MLT) distribution of HLTs based on the OGO 6 data from 1969–1970 and found that the location of HLTs was aligned with the polar cap boundary, associated with the maximum electric convection field, as well as enhancements of soft electron fluxes.

The presence of molecular ions in the terrestrial ionosphere was also confirmed by measurements from the Ion Mass Spectrometer (IMS) on board NASA International Satellite for ionospheric Studies (ISIS 2) (Hoffman, 1970). Deployed on April 1, 1971, ISIS 2 operated in an orbit with an apogee of 1,440 km, a perigee of 1,360 km, and an inclination of 88.1°. The IMS onboard the ISIS 2 was designed to measure the ionic compositions of the ionosphere in the mass range of 1–64 amu. Figure 5 shows such observations during the August 4, 1972 geomagnetic storm (Max Kp = 9, Min Dst = -125 nT) (Hoffman et al., 1974). These measurements indicated that during times of increased geomagnetic activity (Kp = 9), O⁺ and N⁺ have comparable concentrations from 55° latitude to 85° at 1,400 km altitude, while the concentration of NO⁺ and N 2 + reached more than 10³ cm⁻³ and that of O 2 + was ∼ 10³ cm⁻² from 55° latitude to 70°. The ion densities ratio of NO⁺/N⁺ was ∼ 0.015–0.35 during this event. When the spacecraft passed through above 55° latitude region, the molecular ions densities increase from 2×10² to 10³ cm⁻³ and the densities of O⁺ decreased from 3 × 10⁴ to 10⁴ cm⁻³. There are several reasons that could explain the abundance of molecular ions during this time. First, based on the OGO 6 measurements from the neutral mass spectrometer in a similar event, the densities of N₂ at high altitudes increased significantly, and this could provide a potential source of molecular N 2 + ions (Hedin and Reber, 1972). Second, these unexpected enhancements of molecular ion densities had similar locations as those of HLTs observed by OGO 6 satellite (Taylor et al., 1975; Grebowsky et al., 1976; Grebowsky et al., 1983) and thus, the enhancement of soft electron precipitation and rapid loss of O⁺ ions at a time associated with strong electric convection fields could provide an additional source of molecular ions in the topside ionosphere.

The concomitant observations of enhancements in molecular ion densities and HLTs were noted not only during solar maximum by OGO 6, but also during the solar minimum by instruments onboard the Atmosphere Explorer (AE-C) mission. Launched in December 1973, AE-C aimed to study the structure of thermosphere, especially how the photochemical processes govern the region (Richards and Voglozin, 2011). During the first year of operation, the perigee moved from about 68° latitude north down to about 60° south, and the orbit became circular at approximately 390 km altitude (Richards and Voglozin, 2011). The ion mass spectrometers on board the AE-C were a Bennett-type radio frequency ion mass spectrometer (Brinton et al., 1973) and a magnetic ion mass spectrometer (Hoffman et al., 1973), and were employed to measure ion densities.

HLTs were observed during June 1976 at 70° latitude and 300 km altitude in the southern hemisphere during quiet winter time conditions (Brinton et al., 1978). Figure 6 shows the ion densities (bottom panel), electron temperature and energy fluxes (center panel), and the Dst and Kp indices (top; shown for context). It can be seen that at this time the density of NO⁺ reached 2.5 × 10³ cm⁻³, and the density N 2 + and O 2 + were 9.5 × 10² and 5 × 10² cm⁻³. Unlike the depletion of O⁺ in the HLT observed by OGO 6, the observed O⁺ density by AE-C didn’t decrease as the molecular ion densities increased. By examining the electron temperature as well as the energetic particle flux near the HLTs, the increase of electron temperature suggests that the existence of a locally acting heating mechanism responsible for the enhancement in the energetic particle flux. This could possibly have provided the additional energy to molecular ions, leading the formation of HLTs in the high latitude ionosphere (Brinton et al., 1978). Furthermore, O⁺ ions were the dominant heavy ion species above 50° latitude ionosphere and the dominant molecular ions species were either NO⁺ or O 2 + . The NO⁺ ions was likely to dominate the molecular ions species of the sunlit F region as well as 60°–90° latitude in the nightside region, while O 2 + was likely to dominate the nightside region from 50°–60° latitude. Note that N 2 + was never the dominant ion species during solar minimum conditions, but it could be the second most abundant molecular ions species where NO⁺ was the major molecular ion. The highest observed density of O 2 + and NO⁺ were ∼10⁴ cm⁻³ near the cusp region, and ∼10³ cm⁻³ around the nightside auroral zone (Brinton et al., 1978).

The upflowing molecular ions at several thousand kilometers altitude were first observed by Suprathermal Ion Mass Spectrometer (SMS) carried on the Akebono (EXOS-D) spacecraft. Launched on February 21, 1989, the Akebono (EXOS-D) spacecraft was a Japan-led satellite mission designed to investigate processes leading to particle acceleration above the auroral region (Tsuruda and Oya, 1991). The Akebono spacecraft operated in an elliptical polar orbit, with an apogee of 2.65 R E ∼ 10,500 km) altitude, a perigee of 275 km, and inclination of 75°. The SMS on board the Akebono spacecraft was designed to measure mass-per-charge (m/q) and energy-per-charge (E/q) with the range of 1–67 amu/q and 0.1–4,000 eV/q by sampling the two dimensional thermal (0–25.5 eV) and suprathermal (55 eV/q–4.1 keV/q) ion energy distributions in the satellite spin plane (Whalen et al., 1990).

Table 1 summarizes the observations of molecular ions from Akebono spacecraft based on four storm events in 1990 [adapted from Yau et al. (1993)]. Molecular ions were a minor component of the upflowing ionospheric ion population, for which NO⁺ and N 2 + were the dominant molecular ion species, and the density of O 2 + was one order of magnitude lower. Molecular ions could be observed during the storm main and recovery phases at altitudes between 7,000–10,000 km near 70° latitude. The abundance of molecular ions was correlated with the density ratio of N⁺/O⁺ (Yau et al., 1993), that is, the maximum flux of molecular ions was accompanied by the unity ratio of N⁺/O⁺, and the molecular ions flux could be at most 15% of the total ionospheric outflow fluxes during storm time. The increase in molecular ions densities can be explained by the increase in neutrals densities and their collisional ionization in the 500–1,000 km altitude range. For instance, the density of N₂ in this region, as predicted by the Mass-Spectrometer-Incoherent-Scatter (MSIS-86) model (Hedin, 1987), increases by a factor of ∼ 80 from quiet time (Ap Index = 4) to storm time conditions (Ap Index = 60). Moreover, heavy ions produced in the 500–1,000 km altitude region are required to attain ∼ 1 km/s velocities in order to reach the high altitude region. Based on the Akebono spacecraft observational data, the lifetimes of molecular ions between 300 and 1,000 km were estimated ∼ tens of minutes. This implies that transverse heating commonly occurring between 400 and 1,000 km altitude during the active auroral conditions could be sufficient to energize them.

Previous observations indicated that molecular ions were likely to be present in the topside ionosphere, during and after strong geomagnetic storms, for which the minimum Dst was smaller than -100 nT. However, recent observations from the CASSIOPE Enhanced Polar Outflow Probe (e-POP) mission indicated that molecular ions were observed frequently even during modest geomagnetic storm at all e-POP altitudes, spanning between 325–1,500 km (Yau et al., 2006; Yau and Howarth, 2016). Based on the e-POP data collected during 2013–2018 time period, most observations of molecular ions occurred in the pre-midnight sector above 50° latitude ionosphere, while the lowest count rate events were located in the 8–10 MLT range, which coincided with the peak region of energetic precipitating electrons (Foss and Yau, 2019).

Until the flight of the Dynamic Explorer (DE-1), instruments on board magnetospheric missions were not capable of fully resolving all heavy ion species, molecular ions in particular. Explorer 45, launched on November 15, 1971, reported on the presence of an unexpected heavier ion species (M/Q ≥ 9) with energies in the range of tens of MeVs, observed in the radiation belt region during the geomagnetic storm of August 4, 1972 (Max Kp = 9, Min Dst = -125 nT). Because the heavy ion detector telescope on the Explorer 45 didn’t have capability to accurately determine the mass of the observed ion species, Spjeldvik and Fritz (1981) identified these energetic ion species either as the magnesium, or silicon and iron ions.

Molecular N 2 + , NO⁺, and O 2 + ions were first observed in the magnetosphere by the Retarded Ion Mass Spectrometer (RIMS) (Chappell et al., 1982) on board the Dynamic Explorer (DE-1) (Craven et al., 1985). Launched on August 3, 1981, the DE-1 covered the altitude range between 500 km and ∼ 3.6 Earth radii, and aimed to investigate in the interactive processes in the Earth’s ionosphere, plasmasphere, and magnetosphere. RIMS was designed to measure ions with mass between 1 and 32 amu, and with energies ranging from 0 to 50 eV. To resolve molecular ions species and their corresponding kinetic energies, RIMS was designed with the mass voltage steps closer together for mass range between 28 and 32. During the storm of September 6, 1982 (Max Kp = 9, Min Dst = ∼ -300 nT), DE-1 measurements show that the maximum flux of molecular ions was as high as ∼ 10⁶ cm⁻² s⁻¹ around 70° latitude at 1–3 R _E , and NO⁺ and N 2 + were the dominant molecular ions species with similar fluxes. Furthermore, the velocity distribution of molecular ions followed a Maxwellian distribution in the ionosphere, and transferred to the field-aligned velocity distribution at several Earth radii altitude (Craven et al., 1985). In the region between 1–3 R _E , the velocities of molecular ions were observed to be around 5–10 km/s, and their kinetic energies were at least 20 eV at 2.5 R _E geocentric distance. The DE-1 observational dataset suggests that molecular ions are likely to be produced in the polar cusp region and convected to the nightside cusp and polar cap region by the influence of crossed electric and magnetic fields (E × B).

Energetic molecular ions with energies higher than 100 keV/e were first detected in the outer ring current region (L ∼ 7) by Suprathermal Energy ionic Charge Analyzer (SULEICA) onboard the Active Magnetospheric Particle Tracer Explorers (AMPTE) Ion release Module (IRM) spacecraft. Launched on August 16, 1984, the AMPTE/IRM operated in an elliptical orbit with inclination of 28.8° with an apogee of 18.7 R _E (Mobius et al., 1985). The SULEICA instrument was a curved plate electrostatic energy-per-charge analyzer that measured ion energies between 5–270 keV/q (Hausler et al., 1985). While no observations of molecular ion were reported during quiet time periods by the AMPTE/IRM spacecraft, molecular ions in the outer ring current were observed during multiple storm events (Klecker et al., 1986). Table 2 presents a synthesis of measured (NO⁺+ O 2 + )/O⁺ fluxes, and the relevant information regarding each storm interval (Dst, Kp, and observation time interval), as well as the ratio of O⁺ energy flux to the total observed energy flux for these events. The observational record indicates that both O 2 + and NO⁺ were the dominant molecular ions species in this region. The average molecular ions flux was observed to be around 3–4% of O⁺ flux in the energy range 80–230 keV during active times. Figure 7 shows the change in energy flux with particle energy during the early main phase of the September 4, 1984 storm, based on SULEICA measurements (Klecker et al., 1986). Molecular NO⁺ and O 2 + ions (purple) were observed at L ∼ 6.5–7, having energies of the order of 100 keV/e, contributing ∼ 0.5% of the total energy of 32 keV/cm⁻³ in the energy range 20–230 keV/e. These observations of energetic molecular ions suggest that either the mass selection energization mechanisms or the density profile of the thermosphere during the storm time played a significant role in the efficient heating of the molecular ions as they were transported from the ionosphere to the magnetosphere.

Observations of molecular ions at hundreds of Earth radii downtail were first recorded by instruments onboard the Geotail mission (Nishida, 1994). The Suprathermal Ion Composition Spectrometer (STICS) of Geotail/EPIC (Energetic Particles and Ion Composition) instrument and the Low Energy Particle Energy Analyzer (LEP-EA) had the capability to measure ions in the energy range of 9.4–210 keV/e and 0.03–40 keV/e (Christon et al., 1994; Williams et al., 1994). Total kinetic energy, energy-per-charge, and time-of-flight measurements of individual ions are combined with various telescope parameters to generate pulse height analysis (PHAs) events and the count rates of PHAs were related to the abundances of ions in the observed region. Singly charged heavy ions, including atomic N⁺ and O⁺, and molecular N 2 + , NO⁺, and O 2 + ions, were observed in Earth’s magnetotail at distances X ∼ -146 R _E during geomagnetically active times (maximum Kp value was ∼7, minimum Dst was only -40 nT). Figure 8 shows the rest frame phase space ion densities vs. ion velocities based on Geotail observational data. It can be seen that the atomic N⁺ and O⁺ as well as molecular ions had relatively high velocities ∼ 200–900 km/s in the rest frame of the tailward bulk plasma flow, where N⁺/O⁺ = ∼ 25–30% and ( N 2 + +NO⁺+ O 2 + )/O⁺ = ∼ 1–2%. In addition, the molecular ions observed at magnetosphere had similar velocity distribution as the atomic N⁺ and O⁺ in the outer magnetosphere (X ∼ -146 R _E ), but their densities were around two orders of magnitude lower.

Statistical studies based on 20 years of Geotail/STICS data (1995-2015) indicated that the relative abundance of molecular ions in the Earth’s magnetosphere is ∼43% N 2 + , ∼47% NO⁺ and ∼ 10% O 2 + (Christon et al., 2020). Figure 9, adapted from Christon et al. (2020), shows the variation in N⁺ (orange line), O⁺ (blue line) and molecular ions with mass 28 amu (magenta line) and mass 30 amu (purple line) count rates with F10.7 (left panel) and Kp (right panel) indices. These data show that the count rates of magnetospheric molecular ions are the most sensitive to geomagnetic activity, and increase faster with larger values of Kp. Moreover, the count rates of molecular ions and atomic N⁺ and O⁺ ions seem to indicate a different response to the F10.7 index; while the count rates of atomic N⁺ and O⁺ ions proportionally increased with F10.7, that of the molecular ions showed a decline for F10.7 ∼ 120 × 10²² – 220 × 10²² W/m²/Hz, and increased significantly at the highest F10.7.

Molecular ions have also been observed by the Toroidal Imaging Mass-Angle Spectrograph (TIMAS) on board the Polar satellite. Launched on February 24, 1996, the Polar spacecraft measured plasma properties in the polar ionosphere and magnetosphere, aiming to develop an understanding of the deposition of particle energy in the ionosphere and upper atmosphere (Shelley et al., 1995). The Polar spacecraft entered the orbit with an apogee of 9.0 R _E , a perigee of 1.8 R _E , and the inclination of 86°. The Polar/TIMAS instrument aimed to measure particles with energy between 15 eV/e–33 keV/e (Shelley et al., 1995). The mass spectra from TIMAS have been analysed with the help of color-coded count rates versus time and mass step at all energy channels, which allowed the separation of molecular ions from atomic O⁺ and N⁺ ions. However, due to the detection limit of the instrument, for particles with energies below 5 keV/e, the N 2 + , NO⁺, and O 2 + ions were not successfully distinguished (Lennartsson et al., 2000). A statistical study based on the first 22 months of data from TIMAS showed that the energy distribution of molecular ions were identical with O⁺ ions, with the typical energy between 15–110 eV. However, the differential fluxes of molecular ions, ∼ 10⁵ cm⁻²s⁻¹, were two orders of magnitude lower than that of O⁺ ions. Furthermore, the detection frequency of molecular ions was determined to be more sensitive with the enhanced geomagnetic activity, than the O⁺ detection. Therefore, the pathway and energization mechanisms of molecular ions were different from those of O⁺, as they seem to be more specifically associated with enhanced geomagnetic activity (Lennartsson et al., 2000).

Surprisingly, molecular ions had been observed by the Acceleration, Reconnection, Turbulence, and Electrodynamics of the Moon’s Interaction with the Sun (ARTEMIS) spacecraft, whose orbit is centered around the Moon, with periselene between 10–1,000 km and aposelene of 20,000 km (10 lunar radii) (Angelopoulos, 2010). Based on measurements from the electrostatic analyzer (ESA), Poppe et al. (2016) analyzed the ion composition data around 60 R _E away from the Earth during the storm of October 1, 2012 (Max Kp = 7, Min Dst = −122 nT) and storm of February 16, 2014 (Max Kp = 6, Min Dst = −119 nT). This study revealed that the fluxes of molecular ions were on the order of 10⁵–10⁶ cm⁻² s⁻¹, while the proton fluxes were found to yield ∼ 10⁶–10⁸ cm⁻² s⁻¹, suggesting that molecular ions might have comparable velocities with those of protons. These observations of energetic molecular ions from ARTEMIS hint to the connection between Earth’s ionospheric outflow and the composition of lunar exosphere, since the Earth could possibly deliver the nitrogen and oxygen components to the lunar volatile inventory (Poppe et al., 2016).

Recent observations based on the data from the Arase (Exploration of energization and Radiation in Geospace, ERG) satellite reveal frequent presence of molecular ions in the inner magnetosphere during storm times. Launched on December 20, 2016, the Arase (ERG) satellite was designed to directly observe high energy particles in the magnetosphere (Miyoshi et al., 2018). The low-energy particle experiments-ion mass analyzer (LEPi) (Asamura et al., 2018) and medium-energy particle experiments-ion mass analyzer (MEPi) (Yokota et al., 2017) on board the Arase (ERG) satellite were capable of measuring the three-dimensional velocity distribution of ions in the energy range of 0.01–25 keV/q as well as 10–180 keV/q with ions species discrimination, including N⁺⁺/O⁺⁺, N⁺/O⁺, and N 2 + /NO⁺/ O 2 + . Based on the molecular ions measurements by LEPi and MEPi from March to December 2017, including 11 geomagnetic storms, molecular ions were frequently observed at L = 2.5–6.6 with energies above ∼ 12 keV during most magnetic storms, and the average energy density ratio of the molecular ions to O⁺ was found to be ∼ 3% (Seki et al., 2019). The high occurrence rate of molecular ions in the inner magnetosphere indicates that fast ion outflows occur more frequently than expected during the storm time, while previous studies assumed the molecular ions were only observed during intense storms (the minimum Dst ≤ -100 nT).

The convection and energization mechanisms of molecular ions are likely to be different between the high-altitude ionosphere and magnetosphere. The molecular ions were observed to follow the similar energy distribution to O⁺ by the Polar/TIMAS instrument (Lennartsson et al., 2000), but had similar velocity distribution to O⁺ as observed by the Geotail/EPIC instrument and the ARTEMIS spacecraft (Christon et al., 1994; Poppe et al., 2016). In the high-altitude ionosphere, both O⁺ and molecular ions with the escape energy (≥10 eV) can overcome the gravitational bound and flow out the Earth’s ionosphere. Therefore, the energy distribution of these outflowing O⁺ and molecular ions will be likely similar. On the other hand, O⁺ and molecular ions in the magnetotail are possibly energized by the earthward E × B transport, which are charge and mass independent. Thus, O⁺ and molecular ions can likely follow a similar velocity distribution in the magnetotail region.

Instrument limitations on board these spacecrafts brought some difficulties to the study of the cold plasma and the behavior of minor ion species in the ionosphere-magnetosphere system. For example, the minimum detection densities of ions for OGO and AE spacecrafts were 10 cm⁻³ and thus, the region with the molecular ions densities ≤10 cm⁻³ couldn’t be detected. In addition, measurements of cold molecular ions in the magnetosphere are particularly difficult due to spacecraft surface charging, as the ions energy ≤10 eV had the difficulty to be fully resolved by the instruments. Nevertheless, multiple studies report on their occurrence both in the ionosphere and the magnetosphere, spanning a large energy range and radial distances.

Although several observations reveal that molecular ions are frequently observed in the high-latitude ionosphere and the magnetosphere, having energies of the order of eV to keV, the source and energization mechanisms leading to the outflow of these molecular ions in response to various geomagnetic conditions, are not yet fully understood. In this section, we will further explore the source and energization of outflowing molecular ions in the Earth’s ionosphere-magnetosphere system.

Table 3 summarizes the existing observational data sets of molecular ions from past and currently operating spacecraft missions, covering altitudes from few hundred kilometers to hundreds of Earth radii. These observations of molecular ions in the ionosphere-magnetosphere system suggest that:

1. The densities of molecular ions in the polar ionosphere at altitudes between 200–1,000 km were reported to be 0.1–1% of O⁺ densities; however, during geomagnetically active times, the abrupt enhancement of molecular ions densities in the high latitude troughs (whose latitudes were aligned with auroral activity) could reach about 10% of O⁺ ion densities.

Magnetospheric molecular ions were only observed during the storm times, and thus, the observations of molecular ions in the high altitude region are very scarce. This leads to very little knowledge on the convection and energization of molecular ions, causing lack of understanding of their behavior and dynamics both at low and high altitudes. There seems to be an increase in the molecular ions observations in the past 10 years, probably linked to improved mass resolution on instruments flying on current space missions. However, these observational data all occurred at the solar cycle 24, and couldn’t fully represent the molecular ions dynamics in the Earth’s magnetosphere-ionosphere system. Therefore, a dedicated geospace mission that would measure various plasma properties and provide detailed composition in the geospace, at all altitudes, is required in order to understand the relative contributions and the various energization mechanisms of these molecular ions throughout geospace.

Additionally, understanding the sources, energization mechanisms, and the overall dynamics of molecular ions in the magnetosphere-ionosphere system could possibly help understand the impact of the minor heavy ion species in the magnetosphere. Cluster (Haaland et al., 2021) and Geotail (Christon et al., 2017) missions have reported the observations of metal ions in the magnetosphere, but the sources and the transport mechanisms of these metal ions are still largely unknown. This review paper is intended to help inform and guide future ionosphere and magnetosphere studies, and provides context for the available observations of molecular ions. Knowledge of the different behaviors and paths of energization of heavy ions such as N⁺, O⁺, and molecular ions will play a crucial role in the interpretations and analysis of data from many current space missions.