Gas-phase Chromatography Experiments Research Articles

Reactivity of Ts and At oxides and oxyhydrides with a gold surface from periodic DFT calculations.

Adsorption energies, Eads, of oxides and oxyhydrides of the superheavy element (SHEs) Ts and of its lighter homologue At on the gold surface are predicted on the basis of relativistic periodic density functional theory calculations via AMS BAND software. The following compounds were considered: MO, MO2, MOO, and MO(OH) (where M = At and Ts). The aim of this study is to support "one-atom-at-a-time" gas-phase chromatography experiments on reactivity/volatility of SHEs. The results obtained indicate that all the molecules investigated should interact fairly strongly with the gold surface, with those of Ts being more reactive than At ones. The similarity in the Eads values of all the considered At compounds would make it challenging to differentiate between them while measuring their adsorption enthalpies, given experimental uncertainty. However, the difference in Eads among Ts compounds is more pronounced, so that one should be able to differentiate between the species.

A theoretical study of the adsorption behavior of superheavy 7p-elements and their compounds on a surface of gold in comparison with their lighter homologs.

Adsorption energies, Eads, of the 7th row superheavy elements (SHEs) Lv through Og, as well as of the homologous species of the 6th row elements Po through Rn on a gold surface are predicted on the basis of relativistic periodic density functional theory calculations via SCM BAND software. Since some of the elements can also form compounds such as hydrides and oxyhydrides under experimental conditions, the Eads values of the MH (M = Bi/Mc, Po/Lv, At/Ts and Rn/Og) and MOH (M = At/Ts and Rn/Og) molecules on a gold surface were also calculated. The aim of this study is to support "one-atom-at-a-time" gas-phase chromatography experiments on the reactivity/volatility of SHEs. The obtained results show that, in agreement with earlier predictions using somewhat different approaches and with experimental results on Hg, Cn and Rn, the adsorption strength of the elements on the Au(111) surface should follow the sequence: Hg > Fl > Og > Cn ≫ Rn, with the Eads values of less than 100 kJ mol-1. The other elements and their compounds under consideration should adsorb much more strongly on the gold surface with Eads values above 160 kJ mol-1, which should make them indistinguishable with respect to Eads in the chromatography column kept at room temperature and lower. However, with the further detector development, investigations of the chemical properties of these short-lived and less volatile SHEs and their compounds at high temperatures should be possible.

Reactivity of superheavy elements Cn and Fl and of their oxides in comparison with homologous species of Hg and Pb, respectively, towards gold and hydroxylated quartz surfaces.

Adsorption energies, Eads, and other properties of atoms and oxides of the superheavy elements (SHEs) Cn and Fl, as well as of the homologous species of Hg and Pb, on Au(111) and fully hydroxylated quartz surfaces are predicted on the basis of 2c-DFT calculations and a periodic slab model using BAND software. The ambition of the work is to interpret the outcome of "one-atom-at-a-time" gas-phase chromatography experiments on the reactivity/volatility of SHEs. The present results with an improved (dispersion corrected) exchange-correlation functional show that, in agreement with our earlier predictions and experimental results on Pb, Hg and Cn, the sequence of the Eads values of the atoms on the gold surface should be Pb ≫ Hg > Fl > Cn, with rather moderate Eads values smaller than 90 kJ mol-1 (except for that for Pb). Oxides of Hg, Cn and Fl should be much more reactive with the gold surface than the corresponding atoms, with Eads values of about 200 kJ mol-1. A striking difference in the geometry of the deposited oxides was found between group 12 and group 14. An analysis of the Eads values for M and MO (M = Hg/Cn and Pb/Fl) on the hydroxylated α-quartz surface enables one to conclude that atoms of Hg, Cn and Fl should not interact with such a surface at room temperature, while Pb should adsorb on it. Oxides of these elements, on the contrary, should strongly adsorb on quartz with Eads ≥ 100 kJ mol-1. The present theoretical data agree with the experimental results on the elemental species of Hg, Cn and Fl.

Reactivity of the Superheavy Element 115, Mc, and Its Lighter Homologue, Bi, with Respect to Gold and Hydroxylated Quartz Surfaces from Periodic Relativistic DFT Calculations: A Comparison with Element 113, Nh.

Adsorption energies (Eads) of the superheavy element (SHE) Mc, its lighter homologue (Bi), as well as of another superheavy element Nh and some lighter homologues of SHEs on gold and hydroxylated quartz surfaces are predicted via periodic relativistic density functional theory calculations. The aim of this study is to support "one-atom-at-a-time" gas-phase chromatography experiments that are examining the reactivity and volatility of Mc. The obtained Eads values of the Bi and Mc atoms on the Au(111) surface are >200 kJ/mol. On the hydroxylated quartz surface, Mc should adsorb with a minimal energy of 58 kJ/mol. On both types of surfaces, Eads(Mc) should be ∼100 kJ/mol smaller than Eads(Bi) due to strong relativistic effects on its valence 7p electrons. A comparison with other SHEs under investigation shows that Mc should adsorb on gold more strongly than Cn, Nh, and Fl, while on quartz, Mc should adsorb like Nh, with both of them absorbing more strongly than volatile Cn and Fl. The highest reactivity of Mc in the row of the 7p elements is caused by the largest orbital and relativistic destabilization and expansion of the 7p3/2 atomic orbital. Using the calculated Eads, the distribution of the Nh and Mc events in the gas-phase chromatography column with quartz and gold-plated detectors is predicted via Monte Carlo simulations. As a result, Mc atoms should be almost 100% adsorbed in the first section of the chromatography column on quartz, while a few atoms of Nh can reach the second part of the column with gold-plated detectors.

Properties and Reactivity of Hydroxides of Group 13 Elements In, Tl, and Nh from Molecular and Periodic DFT Calculations.

Adsorption energies, Eads, of gaseous hydroxides of In, Tl, and the superheavy element Nh on surfaces of Teflon and gold are predicted using molecular and periodic relativistic DFT calculations. The ambition of the work is to assist related "one atom at a time" gas-phase chromatography experiments on the volatility of NhOH. The obtained low values of Eads(MOH), where M = In, Tl, Nh, on Teflon should guarantee easy transportation of the molecules through the Teflon capillaries from the accelerator to the chemistry setup. Straightforward band-structure DFT calculations using the revPBE-D3(BJ) functional have given an Eads(MOH) value of 161.4 kJ/mol on the Au(111) surface, being indicative of significant molecule-surface interaction. The MOH-gold surface binding is shown to take place via the oxygen atom of the hydroxide, with the oxygen-gold charge density transfer increasing from InOH to NhOH. The trend in Eads(MOH) is shown to be InOH < TlOH < NhOH, caused by increasing molecular dipole moments and decreasing stability of the hydroxides in this row. A trend in Eads of the atoms of these elements on gold is, however, opposite, In > Tl > Nh, caused by the increasing relativistic contraction and stabilization of the np1/2 AO with Z. These opposite trends in Eads(MOH) and Eads(M) in group 13 lead to almost equal Eads(Nh) and Eads(NhOH) values, making identification of Nh, as a type of species, difficult by measuring its adsorption enthalpy on gold.

Carbonyl compounds of Tc, Re, and Bh: Electronic structure, bonding, and volatility

Calculations of molecular properties of M(CO)5 and MH(CO)5, where M = Tc, Re, and Bh, and of the products of their decomposition, M(CO)4 and MH(CO)4, were performed using density functional theory and coupled-cluster methods implemented in the relativistic program suits such as ADF, DIRAC, and ReSpect. The calculated first M-CO bond dissociation energies (FBDEs) of Bh(CO)5 and BhH(CO)5 turned out to be significantly weaker than those of the corresponding Re homologs. The reason for that is the relativistic destabilization and expansion of the 6d AOs, responsible for weaker σ-forth and π-back donations in the Bh compounds. The relativistic FBDEs of M(CO)5 have, therefore, a Λ-shape behavior in the row Tc-Re-Bh, while the non-relativistic values increase toward Bh. Using the results of the molecular calculations and a molecule-slab interaction model, adsorption enthalpies, ΔH ads, of group-7 carbonyl hydrides on quartz and Teflon were estimated for future gas-phase chromatography experiments. It was found that BhH(CO)5 should be almost as volatile as the homologs, although its interaction with the surfaces should be somewhat stronger than that of MH(CO)5 (M = Tc and Re), while the M(CO)4 (M = Tc, Re, and Bh) molecules should be non-volatile. It will, therefore, be difficult to distinguish between the group-7 MH(CO)5 species by measuring their ΔH ads on surfaces of Teflon and quartz with an error bar of ±4 kJ/mol. The trends in properties and ΔH ads of group-7 carbonyl hydrides are similar to those of group-8 carbonyls of Ru, Os, and Hs.

Reactivity of Superheavy Elements Cn, Nh, and Fl and Their Lighter Homologues Hg, Tl, and Pb, Respectively, with a Gold Surface from Periodic DFT Calculations

Adsorption energies of superheavy elements (SHEs) Cn, Nh, and Fl and their lighter homologues Hg, Tl, and Pb, respectively, on a Au(111) surface at different adsorbate coverages are predicted via periodic relativistic DFT calculations with the aim of assisting the outcome of related "one-atom-at-a-time" gas-phase chromatography experiments. In agreement with previous DFT studies with the use of a cluster model, the present results for large supercells are indicative of high volatility of Cn. Thus, this element should not interact with the regular Au(111) surface at room temperature but should adsorb on it in a vacancy. Fl should moderately interact with such a surface under ambient conditions, while Nh should be the most reactive element with respect to gold. All three elements should, however, reveal much lower reactivity toward gold than their lighter homologues. The reasons for this are the strong relativistic stabilization and contraction of the 7s1/2 and 7p1/2 AOs. The obtained trend in the adsorption energy, Nh ≫ Fl > Cn, enables one to easily separate these elements from each other, as well as from their lighter homologues using gold or gold/quartz surfaces.

Electronic structure and properties of MAu and MOH, where M = Tl and Nh: New data

Properties of the MAu and MOH (M = Tl and element 113, Nh) molecules were calculated using the 2c-DFT method. The obtained data are needed for evaluation of reactivity of Nh studied by gas-phase chromatography experiments. Results show that Nh should be less reactive (or more volatile) than Tl, both with respect to gold and the hydroxyl group. The reason for that are strong relativistic effects on the valence 7s and 7p electron shells. In difference to the atoms, NhOH may be less volatile than TlOH due to its larger both dipole moment and anisotropic polarizability.

Penta- and tetracarbonyls of Ru, Os, and Hs: Electronic structure, bonding, and volatility

Calculations of the electronic structures and properties of M(CO)5 and M(CO)4, where M = Ru, Os, and Hs, have been performed using a variety of relativistic methods such as density functional theory and Dirac-Coulomb correlated ones implemented in program packages such as ADF, DIRAC, and ReSpect. The obtained results show that trends in spectroscopic properties of the M(CO)5 species in group 8 follow the same pattern as that of other compounds of group 4 through group 8 elements. The calculated first M–CO bond dissociation energy (FBDE) of Hs(CO)5 turned out to be significantly weaker than that of Os(CO)5. This was obtained both at the scalar relativistic and spin-orbit levels of theory. The reason for that is the relativistic destabilization and the expansion of the 6d AOs, responsible for weaker σ-forth and π-back donations in the Hs compound. Thus, the FBDEs of M(CO)5 have a Λ-shape behavior in the row Ru–Os–Hs. The non-relativistic FBDEs steadily increase in this row. Using the results of the molecular calculations and a molecule-slab dispersion interaction model, the volatility of the group-8 carbonyls was estimated as adsorption enthalpies, ΔHads, on surfaces of quartz and Teflon used in gas-phase chromatography experiments. It was found that Hs(CO)5 should be almost as volatile as the homologs; however, its interaction strength with these surfaces should be somewhat larger than that of both Ru(CO)5 and Os(CO)5, while the M(CO)4 (M = Ru, Os, and Hs) molecules should be non-volatile. It will, therefore, be difficult to distinguish between group-8 M(CO)5 species by measurements of their volatility as ΔHads on inert surfaces with error bars of ∼4 kJ/mol.

Theoretical predictions of properties and volatility of chlorides and oxychlorides of group-4 elements. II. Adsorption of tetrachlorides and oxydichlorides of Zr, Hf, and Rf on neutral and modified surfaces.

With the aim to interpret results of gas-phase chromatography experiments on volatility of group-4 tetrachlorides and oxychlorides including those of Rf, adsorption enthalpies of these species on neutral, and modified quartz surfaces were estimated on the basis of relativistic, two-component Density Functional Theory calculations of MCl4, MOCl2, MCl6(-), and MOCl4(2) with the use of adsorption models. Several mechanisms of adsorption were considered. In the case of physisorption of MCl4, the trend in the adsorption energy in the group should be Zr > Hf > Rf, so that the volatility should change in the opposite direction. The latter trend complies with the one in the sublimation enthalpies, ΔH(sub), of the Zr and Hf tetrachlorides, i.e., Zr < Hf. On the basis of a correlation between these quantities, ΔH(sub)(RfCl4) was predicted as 104.2 kJ/mol. The energy of physisorption of MOCl2 on quartz should increase in the group, Zr < Hf < Rf, as defined by increasing dipole moments of these molecules along the series. In the case of adsorption of MCl4 on quartz by chemical forces, formation of the MOCl2 or MOCl4(2-) complexes on the surface can take place, so that the sequence in the adsorption energy should be Zr > Hf > Rf, as defined by the complex formation energies. In the case of adsorption of MCl4 on a chlorinated quartz surface, formation of the MCl6(2-) surface complexes can occur, so that the trend in the adsorption strength should be Zr ≤ Hf < Rf. All the predicted sequences, showing a smooth change of the adsorption energy in the group, are in disagreement with the reversed trend Zr ≈ Rf < Hf, observed in the "one-atom-at-a-time" gas-phase chromatography experiments. Thus, currently no theoretical explanation can be found for the experimental observations.

Theoretical predictions of properties and volatility of chlorides and oxychlorides of group-4 elements. I. Electronic structures and properties of MCl₄ and MOCl₂ (M = Ti, Zr, Hf, and Rf).

Relativistic, infinite order exact two-component, density functional theory electronic structure calculations were performed for MCl4 and MOCl2 of group-4 elements Ti, Zr, Hf, and element 104, Rf, with the aim to predict their behaviour in gas-phase chromatography experiments. RfCl4 and RfOCl2 were shown to be less stable than their lighter homologs in the group, tetrachlorides and oxychlorides of Zr and Hf, respectively. The oxychlorides turned out to be stable as a bent structure, though the stabilization energy with respect to the flat one (C(2v)) is very small. The trend in the formation of the tetrachlorides from the oxychlorides in group 4 is shown to be Zr < Hf < Rf, while the one in the formation of the oxychlorides from the chlorides is opposite. All the calculated properties are used to estimate adsorption energy of these species on various surfaces in order to interpret results of gas-phase chromatography experiments, as is shown in Paper II.

Theoretical predictions of properties and gas-phase chromatography behaviour of carbonyl complexes of group-6 elements Cr, Mo, W, and element 106, Sg

Fully relativistic, four-component density functional theory electronic structure calculations were performed for M(CO)6 of group-6 elements Cr, Mo, W, and element 106, Sg, with an aim to predict their adsorption behaviour in the gas-phase chromatography experiments. It was shown that seaborgium hexacarbonyl has a longer M-CO bond, smaller ionization potential, and larger polarizability than the other group-6 molecules. This is explained by the increasing relativistic expansion and destabilization of the (n - 1)d AOs with increasing Z in the group. Using results of the calculations, adsorption enthalpies of the group-6 hexacarbonyls on a quartz surface were predicted via a model of physisorption. According to the results, -ΔHads should decrease from Mo to W, while it should be almost equal--within the experimental error bars--for W and Sg. Thus, we expect that in the future gas-phase chromatography experiments it will be almost impossible--what concerns ΔHads--to distinguish between the W and Sg hexacarbonyls by their deposition on quartz.

Theoretical predictions of properties and gas-phase chromatography behaviour of bromides of group-5 elements Nb, Ta, and element 105, Db

Fully relativistic, four-component density functional theory electronic structure calculations were performed for MBr(5), MOBr(3), MBr(6)(-), KMBr(6), and MBr(5)Cl(-) of group-5 elements Nb, Ta, and element 105, Db, with the aim to predict adsorption behaviour of the bromides in gas-phase chromatography experiments. It was shown that in the atmosphere of HBr/BBr(3), the pentabromides are rather stable, and their stability should increase in the row Nb < Db < Ta. Several mechanisms of adsorption were considered. In the case of adsorption by van der Waals forces, the sequence in volatility of the pentabromides should be Nb < Ta < Db, being in agreement with the sublimation enthalpies of the Nb and Ta pentabromides. In the case of adsorption by chemical forces (on a quartz surface modified with KBr∕KCl), formation of the MBr(5)L(-) (L = Cl, Br) complex should occur, so that the volatility should change in an opposite way, i.e., Nb > Ta > Db. This sequence is in agreement with the one observed in the "one-atom-at-a-time" chromatography experiments. Some other scenarios, such as surface oxide formation were also considered but found to be irrelevant.

Relativistic effects on the electronic structure and volatility of group-8 tetroxides MO4, where M=Ru, Os, and element 108, Hs

The influence of relativistic effects on properties and volatility of the group-8 tetroxides MO4, where M=Ru, Os, and element 108, Hs, was studied on the basis of results of the fully relativistic (four component) and nonrelativistic density functional theory calculations. Relativistic effects were shown to increase bond strengths and decrease bond lengths in these molecules. They are responsible for a decrease in molecular polarizabilities and an increase in ionization potentials. The effects are much stronger in HsO4 than in the lighter congeners. Relativistic effects were also shown to slightly decrease dispersion interaction energies of RuO4, OsO4, and HsO4 with an inert (quartz or silicon nitride) surface, i.e., they increase volatility of these compounds as studied in the "one-atom-at-a-time" gas-phase chromatography experiments. They do, however, not influence the trend in group 8: both relativistically and nonrelativistically, volatility should change as RuO4<OsO4<HsO4. The reason for that is identical trends in the relativistic and nonrelativistic space distributions of the valence d electrons.

Predictions of adsorption behaviour of the superheavy element 112

Predictions of chemical behaviour of element 112 with respect to that of Hg for gas-phase chromatography experiments have been made on the basis of fully relativistic four-component Density-Functional Theory (DFT) electronic structure calculations for intermetallic compounds of Hg and element 112. Using a model of localized adsorption, the equilibrium adsorption temperature for element 112 is predicted as somewhat a hundred degrees below that of Hg. This relation should be valid provided experiments are conducted in the same set up, under the same conditions. Thus, the reactivity of element 112 is expected to be somewhere between those of Hg and Rn.

The electronic structure and properties of group 7 oxychlorides, MO3Cl, where M=Tc, Re, and element 107, Bh

Fully relativistic density-functional calculations have been performed for group 7 oxychlorides MO3Cl, where M=Tc, Re, and element 107, Bh. The results have shown the Bh compound to be thermochemically stable and the most stable towards reduction. Due to increasing dipole moments and electric dipole polarizabilities in the group, volatility of the MO3Cl compounds proved to change as TcO3Cl&amp;gt;ReO3Cl&amp;gt;BhO3Cl. For gas-phase chromatography experiments, the adsorption enthalpy of the molecules on the surface of a chromatography column has been predicted as −78±5 kJ/mol.

Gas Phase Chromatography Experiments with Bromides of Tantalum and Element 105

Gas Phase Chromatography Experiments with Bromides of Tantalum and Element 105

Experimental study of gases occluded within microscopic cavities in single crystalline nickel oxide

The existence of microcavities (1–10 μm) in single crystalline nickel oxide was demonstrated by microscopic observations, and their effect on electrical conductivity described elsewhere. It was proposed that the anomalous conductivity values could be attributed to the presence, within the cavities, of oxygen gas under high pressure. In order to confirm this assumption, Raman microprobe and gas-phase chromatography experiments have been performed on NiO single crystals. The results obtained concerning the gases detected (oxygen and nitrogen) are in qualitative and quantitative agreement with the microscopic observations and the electrical conductivity measurements.