Über einige physikalische und chemische Eigenschaften des flüssigen Phosphorwasserstoffs. (Diphosphin P₂H₄)

Abstract

Die bis jetzt durch keine direkte P‐ und H‐Bestimmung erhärtete Formel P2H4 fur das flüssige Phosphin wurde durch eine exakte Molekulargewichtsbestimmung unter Extrapolation auf den idealen Gaszustand bestätigt.

François Joseph Houtou de Labillardière (1796–1867): a Case of Desertion in Nineteenth-Century Chemistry

“…Although the decomposition of diphosphine has been variously interpreted, 66 This process is close to Labillardière's description in the volumetric proportions obtained from PH 3 in relation to the NH 3 used, and in the yellowish deposit obtained, as the compound P 2 H is a solid of this colour that was characterised before 1845. 68 It is therefore evident that the credit for the discovery and characterisation of phosphonium iodide belongs to François Joseph Houtou de Labillardière.…”

Theoretical study of the dipole-bound anion (HPPH3)−

“…We acknowledge, however, that even in such cases where the state would not exist if the dipole potential were ''turned off,'' the static Coulomb stabilization may not be the dominant component of E bind . The system addressed in this study, HPPH 3 Ϫ , is a startling example of the role of electron correlation effects in stabilization of weakly bound electrons.…”

“…The electron binding energy was partitioned into incremental contributions calculated at ''successive'' levels of theory ͓KT, SCF, MPn (nϭ2, 3,4), and CCSD͑T͔͒ and the results for the optimal C s structures of the neutral and the anion are presented in Table II. In the KT approximation, the electron binding energy results from the electrostatic and exchange interactions of the extra electron with the SCF charge distribution of the neutral molecule ͑primarily characterized by the dipole moment, but interactions with higher permanent multipoles and penetration effects are also included͒.…”

“…As Table II shows, the convergence of the MP series for the electron binding energy in HPPH 3 Ϫ is slow. The contribution from ⌬E bind MP3 is negligible, whereas that from ⌬E bind MP4 represents ϳ8% of E bind , and higher-order electron correlation effects, approximated here by ⌬E bind CCSD͑T͒ ͓the difference in the CCSD͑T͒ and MP4 binding energies͔ are very significant, stabilizing, and responsible for ϳ55% of the net electron binding energy and produce our final prediction for E bind ϭ333 cm Ϫ1 .…”

“…Diphosphine and its tautomer Diphosphine (P 2 H 4 ), known since 1844, is one of the simplest phosphorus compounds 1,2 as reported in the early literature. 3 Although some of its properties have been determined experimentally, [1][2][3][4][5][6][7][8][9][10][11][12][13] and theoretically, [14][15][16][17][18][19][20][21][22][23][24] the tautomer HPPH 3 ͑see Fig. 1͒ has been neither reported experimentally nor studied theoretically up to the mid 1990s, when Rak et al 25 undertook theoretical studies on the structure, stability, and reactivity of P 2 H 4 .…”