Peter C. Burgers, Lona Zeneyedpour, Theo M. Luider, John L. Holmes
{"title":"碱砹化物的热力学和物理化学性质的估计:关于分子砹(At2)的键强度和砹化物(At-)的水合焓。","authors":"Peter C. Burgers, Lona Zeneyedpour, Theo M. Luider, John L. Holmes","doi":"10.1002/jms.5010","DOIUrl":null,"url":null,"abstract":"<p>The recent accurate and precise determination of the electron affinity (<i>EA</i>) of the astatine atom At<sup>0</sup> warrants a re-investigation of the estimated thermodynamic properties of At<sup>0</sup> and astatine containing molecules as this <i>EA</i> was found to be much lower (by 0.4 eV) than previous estimated values. In this contribution we estimate, from available data sources, the following thermodynamic and physicochemical properties of the alkali astatides (MAt, M = Li, Na, K, Rb, Cs): their solid and gaseous heats of formation, lattice and gas-phase binding enthalpies, sublimation energies and melting temperatures. Gas-phase charge-transfer dissociation energies for the alkali astatides (the energy requirement for M<sup>+</sup>At<sup>−</sup> ➔ M<sup>0</sup> + At<sup>0</sup>) have been obtained and are compared with those for the other alkali halides. Use of Born-Haber cycles together with the new <i>AE</i> (At<sup>0</sup>) value allows the re-evaluation of Δ<i>H</i><sub><i>f</i></sub> (At<sup>0</sup>)<sub>g</sub> (=56 ± 5 kJ/mol); it is concluded that (At<sub>2</sub>)<sub>g</sub> is a weakly bonded species (bond strength <50 kJ/mol), significantly weaker bonded than previously estimated (116 kJ/mol) and much weaker bonded than I<sub>2</sub> (148 kJ/mol), but in agreement with the finding from theory that spin-orbit coupling considerably reduces the bond strength in At<sub>2</sub>. The hydration enthalpy (Δ<i>H</i><sub><i>aq</i></sub>) of At<sup>−</sup> is estimated to be −230 ± 2 kJ/mol (using Δ<i>H</i><sub><i>aq</i></sub>[H<sup>+</sup>] = −1150.1 kJ/mol), in good agreement with molecular dynamics calculations. Arguments are presented that the largest alkali halide, CsAt, like the smallest, LiF, will be only sparingly soluble in water, following the generalization from hard/soft acid/base principles that “small likes small” and “large likes large.”</p>","PeriodicalId":16178,"journal":{"name":"Journal of Mass Spectrometry","volume":null,"pages":null},"PeriodicalIF":1.9000,"publicationDate":"2024-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jms.5010","citationCount":"0","resultStr":"{\"title\":\"Estimation of thermodynamic and physicochemical properties of the alkali astatides: On the bond strength of molecular astatine (At2) and the hydration enthalpy of astatide (At−)\",\"authors\":\"Peter C. Burgers, Lona Zeneyedpour, Theo M. Luider, John L. Holmes\",\"doi\":\"10.1002/jms.5010\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The recent accurate and precise determination of the electron affinity (<i>EA</i>) of the astatine atom At<sup>0</sup> warrants a re-investigation of the estimated thermodynamic properties of At<sup>0</sup> and astatine containing molecules as this <i>EA</i> was found to be much lower (by 0.4 eV) than previous estimated values. In this contribution we estimate, from available data sources, the following thermodynamic and physicochemical properties of the alkali astatides (MAt, M = Li, Na, K, Rb, Cs): their solid and gaseous heats of formation, lattice and gas-phase binding enthalpies, sublimation energies and melting temperatures. Gas-phase charge-transfer dissociation energies for the alkali astatides (the energy requirement for M<sup>+</sup>At<sup>−</sup> ➔ M<sup>0</sup> + At<sup>0</sup>) have been obtained and are compared with those for the other alkali halides. Use of Born-Haber cycles together with the new <i>AE</i> (At<sup>0</sup>) value allows the re-evaluation of Δ<i>H</i><sub><i>f</i></sub> (At<sup>0</sup>)<sub>g</sub> (=56 ± 5 kJ/mol); it is concluded that (At<sub>2</sub>)<sub>g</sub> is a weakly bonded species (bond strength <50 kJ/mol), significantly weaker bonded than previously estimated (116 kJ/mol) and much weaker bonded than I<sub>2</sub> (148 kJ/mol), but in agreement with the finding from theory that spin-orbit coupling considerably reduces the bond strength in At<sub>2</sub>. The hydration enthalpy (Δ<i>H</i><sub><i>aq</i></sub>) of At<sup>−</sup> is estimated to be −230 ± 2 kJ/mol (using Δ<i>H</i><sub><i>aq</i></sub>[H<sup>+</sup>] = −1150.1 kJ/mol), in good agreement with molecular dynamics calculations. 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Estimation of thermodynamic and physicochemical properties of the alkali astatides: On the bond strength of molecular astatine (At2) and the hydration enthalpy of astatide (At−)
The recent accurate and precise determination of the electron affinity (EA) of the astatine atom At0 warrants a re-investigation of the estimated thermodynamic properties of At0 and astatine containing molecules as this EA was found to be much lower (by 0.4 eV) than previous estimated values. In this contribution we estimate, from available data sources, the following thermodynamic and physicochemical properties of the alkali astatides (MAt, M = Li, Na, K, Rb, Cs): their solid and gaseous heats of formation, lattice and gas-phase binding enthalpies, sublimation energies and melting temperatures. Gas-phase charge-transfer dissociation energies for the alkali astatides (the energy requirement for M+At− ➔ M0 + At0) have been obtained and are compared with those for the other alkali halides. Use of Born-Haber cycles together with the new AE (At0) value allows the re-evaluation of ΔHf (At0)g (=56 ± 5 kJ/mol); it is concluded that (At2)g is a weakly bonded species (bond strength <50 kJ/mol), significantly weaker bonded than previously estimated (116 kJ/mol) and much weaker bonded than I2 (148 kJ/mol), but in agreement with the finding from theory that spin-orbit coupling considerably reduces the bond strength in At2. The hydration enthalpy (ΔHaq) of At− is estimated to be −230 ± 2 kJ/mol (using ΔHaq[H+] = −1150.1 kJ/mol), in good agreement with molecular dynamics calculations. Arguments are presented that the largest alkali halide, CsAt, like the smallest, LiF, will be only sparingly soluble in water, following the generalization from hard/soft acid/base principles that “small likes small” and “large likes large.”
期刊介绍:
The Journal of Mass Spectrometry publishes papers on a broad range of topics of interest to scientists working in both fundamental and applied areas involving the study of gaseous ions.
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