Small-Angle Neutron Scattering Study on Aggregation of 1-Alkyl-3-methylimidazolium Based Ionic Liquids in Aqueous Solution

Aggregation structures of 1-alkyl-3-methylimidazolium based ionic liquids (ILs) in aqueous solution were investigated by small-angle neutron scattering (SANS) from the viewpoint of alkyl chain length, n, and anions (Cl^?, Br^? and trifluoromethanesulfonate, $ {\text{CF}}_{3} {\text{SO}}_{3}^{ - } $ ). In [C₄mIm⁺]-based IL systems, no noticeable SANS intensity was observed for all of the systems examined here, although aqueous [C₄mIm⁺][ $ {\text{BF}}_{4}^{ - } $ ] solutions show a significant SANS profile originating from concentration fluctuations in the solution (Almasy et al. J Phys Chem B 112:2382–2387, 2008). This suggests that [C₄mIm⁺][Cl^?], [C₄mIm⁺][Br^?] and [C₄mIm⁺][ $ {\text{CF}}_{3} {\text{SO}}_{3}^{ - } $ ] homogeneously mix with water, unlike the [C₄mIm⁺][ $ {\text{BF}}_{4}^{ - } $ ] system, due to preferential hydration of the ions. In the case of the C _n mIm cations with longer alkyl chain lengths (n = 8 and 12), SANS profiles were clearly observed in the aqueous solutions at IL concentrations of C _IL > 230 and 20.0 mmol·dm^?3, respectively. For aqueous [C₈mIm⁺][Br^?] solutions, the asymptotic behavior of the scattering function varied largely from I(q) ~ q ^?2 to ~q ^?4 with increasing C _IL, indicating that the solution changes from an inhomogeneous mixing state to a nano-scale micelle state. Aqueous [C₁₂mIm⁺][Br^?] solutions show a typical SANS profile for micelle formation in solution. It was found from a model-fitting analysis that the structure of the [C₁₂mIm⁺][Br^?] micelle is ellipsoidal, not spherical, in solutions over the C _IL range examined here.     

Size effect on thermodynamic parameters for the peanut-like CaMoO4 micro/nano reaction systems

Peanut-like CaMoO₄ micro/nano structures with three different sizes were harvested by a simple reverse-microemulsion method at room temperature. Employing synthesized micro/nano CaMoO₄ and HCl as reaction systems, thermodynamic parameters such as standard molar enthalpy of reaction Δ_r H _m ^θ , standard molar Gibbs free energy of activation Δ _r ^≠ G _m ^θ , standard molar enthalpy of activation Δ _r ^≠ H _m ^θ , and standard molar entropy of activation Δ _r ^≠ S _m ^θ were successfully acquired for the first time by in situ microcalorimetry. Furthermore, change regularities of the thermodynamic parameters for the micro/nano reaction systems were obtained and discussed. It demonstrated that size effect has significant influence on thermodynamic parameters of micro/nano material reaction systems.     

A theoretical study of internal rearrangements and open channels for fission and mass exchanges in Xe n + clusters

In a previous work the equilibrium geometrical and electronic structures of Xe _n ⁺ clusters had been established using a non-empirical model hamiltonian. The same model is used to determine the energetic barriers between the nearly degenerate isomers; the movement of the neutral atoms around the Xe ₃ ⁺ or Xe ₄ ⁺ ionized linear cores are quite easy (ΔE?0.9 kcal/mole), the changes from a Xe ₃ ⁺ to a Xe ₄ ⁺ core are more difficult (ΔE?2.0 kcal/mole). The energetically possible fissions from a vertical photoionization \(Xe_n \xrightarrow{{h v}}Xe_n^{v + } \to Xe_p^ + + Xe_{n - p} \) forn≦19,p=1–9 and 12–14 and mass exchanges Xe _p ⁺ +Xe _q →Xe _p+m ⁺ +Xe _q?m (m=1,2,3) from relaxed Xe _p ⁺ clusters are given forp+m≦9 and 12–14 andq≦19. Surprisingly the reverse reactions are shown to occur for some values ofp andq. Numerous processes lead to Xe ₁₃ ⁺ , which is especially stable.     

Energies of the gas-phase deprotonation of nitro-substituted benzenesulfonic and benzoic acids: The role of the conformation isomerism of sulfonic acids

The Gibbs energies of deprotonation Δ_r G ₂₉₈ ^○ of gaseous benzoic acid (BA), benzenesulfonic acid (BSA) and their six mono-, di-, and trinitro-substituted derivatives are calculated by means of B3LYP/cc-pVTZ and MP2/6-311++G**. The dependences of Δ_r G ₂₉₈ ^○ on the number and the position of nitro groups in an aromatic ring are revealed, as is the possibility of intramolecular hydrogen bond (IHB) formation in ortho-substituted acids. It is found that the deprotonation of conformers of ortho-nitro-substituted BSA without IHBs requires less energy (by 4–5 kcal/mol) than for conformers with IHBs. It is shown that the Δ_r G ₂₉₈ ^○ values for substituted BA are ～22 kcal/mol higher than the corresponding values for substituted BSA. A trend of diminishing Δ_r G ₂₉₈ ^○ for nitro-substituted acids is observed when the number of nitro groups is increased, and di- and trinitro-substituted BSA may therefore be considered superstrong acids.     

Activation parameters of supercritical and gas-phase β-pinene thermal isomerization

New data on enthalpy and entropy contributions to the energy barrier of β-pinene thermal isomerization were obtained. The rate of β-pinene conversion is higher in supercritical EtOH (P = 120 atm) than in the gas phase (P ≤ 1 atm, without solvent, or for inert carrier gas N₂) at equal temperatures. The highest activation energy E _Σ of total β-pinene conversion is also observed in reactions in the supercritical (sc) condition. Activation parameters ΔH _Σ ^# , ΔS _Σ ^# , and ΔG _Σ ^# depend strongly on the reaction pressure. Thus, at P ≤ 1 atm (gas-phase reaction) the values of ΔS _Σ ^# are negative, while at sc conditions at P = 120 atm is positive. The linear dependences lnk _Σ0 ? E _Σ and ΔS _Σ ^# ? ΔS _Σ ^# indicate an isokinetic relation (IKR) and enthalpy-entropy compensation effect (EEC). The isokinetic temperature was calculated (T _iso = 605.5 ± 22.7 K). It was shown that elevation of temperature reduces the value of ΔG _Σ ^# (T) upon sc thermolysis only, whereas in all gas-phase reactions ΔG _Σ ^# (T) increases. At equal reaction temperatures, the greatest values of K _eq ^# (T) proved to be typical for thermolysis in sc-EtOH. We hypothesize that the rate of total β-pinene conversion increases dramatically due to a considerable shift in equilibrium toward higher concentrations of activated complex y _TS ^# . A detailed analysis of activation parameters shows that the IKR and EEC coincide, evidence of a common mechanism of β-pinene conversion observed under different reaction conditions, including thermolysis in sc-EtOH.     

Dichlorotriethylphosphine-[N-formyl-N,N′-bis(3,4-dimethoxy)benzyl-trimethylenediamine] platinum(II)

By treatment of 1,3-bis(3,4-dimethoxybenzyl)-3,4,5,6-tetrahydropyrimidinium chloride (1) with KOBu ^t and [PtCl₂(PEt₃)₂]₂ N-coordinated platinum complex (2) is obtained. The Pt atom is coordinated in square planar arrangements by two chloride ions in a trans-configuration, the N-formyl-N,N′-bisaryltrimethylenediamine nitrogen atom, and the phosphine P atom. An extensive three-dimensional network of three C-H…O hydrogen bonds, two C-H…π and one π…π interactions are responsible for the crystal stabilization. Intermolecular hydrogen bonds and C-H…π interactions produce R ₂ ² (6), R ₂ ² (22), R ₂ ² (24), R ₃ ³ (23), R ₄ ⁴ (26), and R ₄ ⁴ (32) rings.     

Pressure and isotope effects on the proton jump of the hydroxide ion at 25°C

The limiting molar conductances Λ⁰ of potassium deuteroxide KOD in D₂O and potassium hydroxide KOH in H₂O were determined at 25°C as a function of pressure to disclose the difference in the proton-jump mechanism between an OH^? (OD^?) and a H₃O⁺ (D₃O⁺) ion. The excess conductance of the OD^? ion in D₂O λ _E ^O (OD ^-), as estimated by the equation $$\lambda _E^O (OD^ - ) = \Lambda ^O (KOD/D_2 O) - \Lambda ^O (KCl/D_2 O)$$ increases a little with pressure as well as the excess conductance of the OH^? ion in H₂O $$\lambda _E^O (OH^ - ) = \Lambda ^O (KOH/H_2 O) - \Lambda ^O (KCl/H_2 O)$$ However, their rates of increase with pressure are much smaller than those of the excess deuteron and proton conductances, λ _E ^O (D ⁺) and λ _E ^O (H ⁺). With respect to the isotope effect on the excess conductance, λ _E ^O (OH ^-)/λ _E ^O (D ⁺) decreases with presure as in the case of λ _E ^O (H ⁺)/λ _E ^O (D ⁺), but the value of λ _E ^O (OH ^-)/λ _E ^O (OD ^-) itself is much larger than that of λ _E ^O (H ⁺)/λ _E ^O (D ⁺) at each pressure. These results are ascribed to the difference in the pre-rotation of water molecules, which is brought about by the difference in the intial orientation of the rotating water molecule adjacent to the OH^? (OD^?) or the H₃O⁺ (D₃O⁺) ion.     

Thermodynamic transfer functions for urea and thiourea from water to water-tetrahydrofuran mixtures from precise vapor-pressure measurements

The rate of change of the standard chemical potential with solvent composition, \(\partial \bar G_0 /\partial Z\) , has been calculated from precise vapor-pressure measurements for urea at three temperatures and for thiourea at 298.15°K in water-tetrahydrofuran (THF) mixtures. From these results the standard free energy of transfer ΔG _t ^o of the solutes from water to various water-THF mixtures has been obtained together with the standard molar entropy ΔS _t ^o and the standard molar enthalpy ΔH _t ^o of transfer at 298.15°K in the case of urea. The quantity ΔG _t ^o for urea is negative in the water-rich region and positive for mole fractions THF>0.2. There is a nearly complete compensation between ΔH _t ^o andTΔS _t ^o at 298.15°K up to mole fraction THF=0.5. These phenomena can be partly related to the structure in H₂O-THF mixtures.     

Study of ionic equilibria and computation of thermodynamic characteristics of heteropoly anion formation in GdW10O 36 9− solution

Interaction in GdW₁₀O ₃₆ ^9? -H⁺(OH^?)-H₂O system ( \(C_{GdW_{10} O_{36}^{9 - } } \) = 1 × 10^?3 mol/L) was studied by pH potentiometry at 25 ± 0.1°C, and a model that describes equilibrium processes in acid and alkaline regions was selected. Logarithms of concentrational and thermodynamic constants, values of Gibbs energy of monomeric ions reactions, and standard Gibbs energies of formation (ΔG _f ^o ) of heteropoly anions H _n GdW₁₀O ₃₆ ^(9?n)? and H _m GdW₅O ₁₈ ^(3?n)? were calculated. A series-parallel scheme of ion transitions was pro-posed, ion distribution diagrams in aqueous solutions were built, the regions of preferable anion content were found, and heteropoly salts were synthesized.     

Vapor pressure isotope effects in aqueous systems. VIII. The system dimethyl sulfoxide/H2O/D2O

Vapor pressures for the system I (dimethyl sulfoxide/H₂O=DMSO/H₂O) and isotopic differential pressures I-II (II=DMSO/D₂O) have been measured between 25 and 70°C at DMSO concentrations of 0.05, 0.15, 0.30, 0.45, 0.60, 0.70, 0.80, 0.87, and 0.92 mole fraction. A high-precision differential method was used. The total pressures over the solutions, I, have been fitted to a relation derived from the Duhem-Margules equation, P ^T =P ₁ ^o X₁γ₁+P ₂ ^o X₂γ₂, with γ₁=exp[∑_kα_kX ₂ ^k ] and $$\gamma _2 = exp[\sum \alpha _k X_2^k - \sum (\alpha _k /(k - 1))(kX_2^{k - 1} - 1)].$$ . The α_k are parameters andk is a number ≥2. The α_k were taken as temperature dependent. Four parameters sufficed to fit the data within experimental error. Excess partial molal properties derived from the fits are in quantitative agreement with earlier literature results derived from the directly measured partial pressures, but the present data extend over a wider temperature range. The isotopic differential pressures I-II were similarly fitted to the relation above. The excess free energies and enthalpiesG _I ^E andH _I ^E are large and negative. The isotope effects ΔG _I,II ^E =G _I ^E ?G _II ^E and ΔH _I,II ^E are negative. They are discussed in detail in terms of the theory of isotope effects in condensed phases and demonstrated to be consistent with that theory and with the available spectroscopic data. A small amount of enthalpy data for the solution of DMSO in HOH and DOD is reported.     

Study of compatibility in polymeric system cellulose nitrate-cellulose acetate by reversed-phase gas chromatography

Therm odynamic compatibility in the polymeric system cellulose nitrate-cellulose acetate is studied by reversed-phase gas chromatography. The excess enthalpy ΔH _ji ^E , entropy ΔS _ji ^E , and Gibbs energy ΔG _ji ^E of mixing of the components, and also the Flory-Huggins interaction parameter χ_ji are estimated.     

Analytical photoion spectroscopy applied to dissociative single and double photoionization of diatomic molecules (H2, N2, O2, CO,and NO)

This work reports the principle, advantage, and limitations of analytical photoion spectroscopy which has been applied to dissociative photoionization processes for diatomic molecules such as H₂, N₂, CO, and NO. Characteristic features observed in the differential photoion spectra are summarized with a focus on (pre)dissociation of(i) multielectron excitation states commonly observed in the inner valence regions,(ii) shape resonances, and(iii) doubly charged parent ions. Possible origins for negative peaks in the differential spectra are discussed. This spectroscopy is applied to the reported photoion branching ratios for D₂ (and H₂ at high energies). The main findings are as follows: (1) The direct dissociation of theX ²Σ _g ⁺ (1sσ _g ) state of D ₂ ⁺ , the two-electron excited state¹Σ _u ⁺ (2pσ _u 2sσ _g ) of D₂, and the²Σ _u ⁺ (2pσ _u ) state of D ₂ ⁺ appear clearly in the differential spectrum, as previously observed for H₂. (2) Decay of H ₂ ⁺ (D ₂ ⁺ ) to H⁺ (D⁺) above 38 eV is due to the direct dissociation of highly excited states of H ₂ ⁺ (D ₂ ⁺ ) such as the²Σ _g ⁺ (2sσ _g ) and high-lying Rydberg states converging on H ₂ ²⁺ (D ₂ ²⁺ ). (3) In the ionization continuum of H ₂ ²⁺ (D ₂ ²⁺ ) peculiar dissociation pathways are observed. The differential photoion spectra for O₂ derived from the reported photoion branching ratios are also presented. The (pre)dissociation of theb ⁴Σ _g ^? ,B ²Σ _g ^? , III²Π _u ,²Σ _u ^? , and^2,4Σ _g ^? states of O ₂ ⁺ appears as the corresponding positive values in the spectra in accord with previous observations. Some other dissociation pathways possibly contributing to the spectra are discussed including dissociative double ionization.     

Guided ion beam studies of the reactions of O+, O 2 + , N+ and N 2 + with silane

Guided ion beam mass spectrometry is used to measure the cross sections as a function of kinetic energy for reaction of SiH₄ with O⁺(⁴S), O ₂ ⁺ (²Π_g,v=0), N⁺(³P), and N ₂ ⁺ (²Σ _g ⁺ ,v=0). All four ions react with silane by dissociative charge-transfer to form SiH _m ⁺ (m=0?3), and all but N ₂ ⁺ also form SiXH _m ⁺ products where (m=0?3) andX=O, O₂ or N. The overall reactivity of the O⁺, O ₂ ⁺ , and N⁺ systems show little dependence on kinetic energy, but for the case of N ₂ ⁺ , the reaction probability and product distribution relies heavily on the kinetic energy of the system. The present results are compared with those previously reported for reactions of the rare gas ions with silane [13] and are discussed in terms of vertical ionization from the 1t ₂ and 3a ₁ bands of SiH₄. Thermal reaction rates are also provided and dicussed.     

Spectroscopic properties of the Ar 2 * (5p) excimer states

The transitions between Ar ₂ ^* (5p) and Ar ₂ ^* (4sΣ _u) have been investigated by absorption spectrometry. The fine structure of the Ar ₂ ^* (5p ³ Π _g) was attributed to a predominantly Hund’s case a coupling. A spin orbit coupling constant of A = (9.8±0.3) cm^-1 results. Absorption by the singlet system allows one to determine the triplet/singlet splitting between the Ar ₂ ^* (4s Σ _u) states to be (540 ± 100) cm^-1. The transition probabilities of the Ar ₂ ^* (5p) and Ar ₂ ^* (6p) levels were determined by saturation spectrometry yielding values between (0.2–2.5) · 10⁶ s^-1.     

The Standard Chemical-Thermodynamic Properties of Phosphorus and Some of its Key Compounds and Aqueous Species: An Evaluation of Differences between the Previous Recommendations of NBS/NIST and CODATA

The aqueous chemistry of phosphorus is dominated by P(V), which under typical environmental conditions (and depending on pH and concentration) can be present as the orthophosphate species H₃PO ₄ ⁰ (aq),H₂PO ₄ ^? (aq),HPO ₄ ^2? (aq) or PO ₄ ^3? (aq). Many divalent, trivalent and tetravalent metal ions form sparingly soluble orthophosphate phases that, depending on the solution pH and concentrations of phosphate and metal ions, can be solubility limiting phases. Geochemical and chemical engineering modeling of solubilities and speciation require comprehensive thermodynamic databases that include the standard thermodynamic properties for the aqueous species and solid compounds. The most widely used sources for standard thermodynamic properties are the NBS (now NIST) Tables (from 1982 and earlier, with a 1989 erratum) and the final CODATA evaluation (1989). However, a comparison of the reported enthalpies of formation and Gibbs energies of formation for key phosphate compounds and aqueous species, especially H₂PO ₄ ^? (aq) and HPO ₄ ^2? (aq), shows a systematic and nearly constant difference of 6.3 to 6.9 kJ?mol^?1 per phosphorus atom between these two evaluations. The existing literature contains numerous studies (including major data summaries) that are based on one or the other of these evaluations. In this report we examine and identify the origin of this difference and conclude that the CODATA evaluation is more reliable. Values of the standard entropies of the H₂PO ₄ ^? (aq) and HPO ₄ ^2? (aq) ions at 298.15 K and p?° =1 bar were re-examined in the light of more recent information and data not considered in the CODATA review, and a slightly different value of S _m ^o (H₂PO ₄ ^? , aq, 298.15 K) = (90.6±1.5) J?K^?1?mol^?1 was obtained.     

Bond dissociation energies and bond orders for diatomic alkali halides

The bond dissociation energies for Alkali halides have been estimated based on the derived relations: $$\begin{gathered} D_{AB} = \bar D_{AB} + 31.973{\text{ e}}^{0.363\Delta x} {\text{ and}} \hfill \\ D_{AB} = \bar D_{AB} (1 - 0.2075\Delta xr_e ) + 52.29\Delta x, \hfill \\ \end{gathered} $$ where \(\bar D_{AB} = (D_{AA} \cdot D_{BB} )^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-0em} 2}} \) , Δx represents Pauling electronegativity differences x(_A ?x_B) and r _e is the internuclear distance. A simplified formula relating bond orders, q, to spectroscopic constants is suggested. The formula has the form q = 1.5783 × 10^?3 (ω _e ² r_e/ B_e)^1/2. The ambiguity arising from the Parr and Borkman relation is discussed. The present study supports the view of Politzer that q/(0.5r _e)² is the correct definition of bond order. The estimated bond energies and bond orders are in reasonably good agreement with the literature values. The bond energies estimated with the relations we suggested, for alkali halides give an error of 4.5% and 5.3%, respectively. The corresponding error associated with Pauling's equation is 40.2%.     

The interaction of metastable helium atoms with alkali atoms

Using crossed beams of ground state alkali atoms A (A = Li, Na, K, Rb, Cs) and metastable He(2³ S), He(2¹ S) atoms, we have measured the energy spectra of electrons resulting in the respective Penning ionization processes at: thermal collision energies. The data are interpreted to yield the well depthD _e ^* of the²Σ interaction potentials as follows: He(2³ S)+A:D _e ^* (A=Li)=868(20) meV;D _e ^* (Na)=740(25) meV;D _e ^* (K)=591(24) meV;D _e ^* (Rb)=546(18) meV;D _e ^* (Cs)=533(18) meV. He(2¹ S)+A:D _e ^* (Li)=330(17) meV;D _e ^* (Na)=277(24) meV;D _e ^* (K)=202(23) meV;D _e ^* (Rb)=219(18) meV;D _e ^* (Cs)=277(18) meV. The well depth for He(2³ S)+A(²Σ) is always close to 80% of the well depth for Li(2s)+A(X ¹Σ). The ionization cross sections for He(2¹ S)+A are about 3 to 4 times larger than those for He(2³ S)+A.     

Quantum chemical DFT calculations of the local structure of the hydrated electron and dielectron

The adiabatic bound state of an excess electron is calculated for a water cluster (H₂O) ₈ ^? in the gas phase using the DFT-B3LYP method with the extended 6-311++G(3df,3pd) basis set. For the liquid phase the calculation is performed in the polarizable continuum model (PCM) with regard to the solvent effect (water, ? = 78.38) in the supermolecule-continuum approximation. The value calculated by DFT-B3LYP for the vertical binding energy (VBE) of an excess electron in the anionic cluster (VBE(H₂O) ₈ ^? = 0.59 eV) agrees well with the experimental value of 0.44 eV obtained from photoelectron spectra in the gas phase. The VBE value of the excess electron calculated by PCM-B3LYP for the (H₂O) ₈ ^? cluster in the liquid phase (VBE = 1.70 eV) corresponds well to the absorption band maximum λ_max = 715 nm (VBE = 1.73 eV) in the optical spectrum of the hydrated electron hydr e _hydr ^? . Estimating the adiabatic binding energy (ABE)e _hydr ^t- in the (H₂O) ₈ ^? cluster (ABE = 1.63 eV), we obtain good agreement with the experimental free energy of electron hydration ΔG ₂₉₈ ⁰ (e _hydr ^? ) = 1.61 eV. The local model (H₂O) ₈ ^2? of the hydrated dielectron is considered in the supermolecule-continuum approximation. It is shown that the hydrated electron and dielectron have the same characteristic local structure: -O-H{↑}H-O- and -O-H{↑↓}H-O-respectively.     

The thermodynamic parameters of oxygen nonstoichiometry defects in lanthanum cobaltite doped with acceptor impurities (Sr and Ni)

The oxygen nonstoichiometry δ of lanthanum cobaltite doped with acceptor impurities (Sr and Ni), La_{1 ? x} Sr_xCo_0.9Ni_0.1O_{3 ? δ} (x = 0.1, 0.3), was studied by high-temperature thermogravimetry over the temperature and pressure ranges 723 K ≤ T ≤ 1373 K and 10^?3 atm ≤ $p_{O_2 } $ ≤ 1 atm. The partial replacement of cobalt with nickel and lanthanum with strontium increased the oxygen nonstoichiometry δ. The partial molar enthalpies $\Delta \bar H^\circ _O $ and entropies $\Delta \bar S^\circ _O $ of solution of oxygen in the solid phase were calculated. Models of point defect formation were suggested and analyzed. The equilibrium constants of formation and concentrations of predominant point defects, ionized oxygen vacancies V _o ^.. , holes Me _Co ^. (Co _Co ^. and Ni _Co ^. ), and electrons Me _Co ^′ (Co _Co ^′ and Ni _Co ^′ ) localized on 3d transition metals, were determined by nonlinear regression from the experimental and theoretical logp $p_{O_2 } $ ?δ dependences.     

Ab initio calculation of the vertical excitation energies of small helium cluster ions

Quantum chemical ab initio calculations have been performed for the vertical excitation energies and oscillator strengths of all low-lying electronically excited states of small helium cluster ions, He _n ⁺ ,n=2, ..., 7. The geometrical structures of the ions were fixed at the equilibrium geometries of the respective ground states, for He ₄ ⁺ and He ₅ ⁺ also one alternative structure was considered. The low-lying excited states can be classified into two categories: the electronic transition can occur either within the central He ₂ ⁺ or He ₃ ⁺ unit or from the peripheral weakly bound He atoms to this unit. The latter transitions are very weak (f≈0.001), closely spaced, with vertical excitation energies of about 5.7 eV. The He ₂ ⁺ and He ₃ ⁺ units have strong transitions at 9.93 and 5.55 eV, respectively; these transitions are only slightly blue-shifted if He ₂ ⁺ or He ₃ ⁺ are placed as “chromophores” into the centre of a larger He _n ⁺ cluster. The large difference in the vertical excitation energy of the strong transition should enable an experimental decision of the question whether the cluster ions have He ₂ ⁺ or He ₃ ⁺ cores.