Gas-Phase Preparation of Subvalent Germanium Monoxide (GeO, X¹Σ⁺) via Non-Adiabatic Reaction Dynamics in the Exit Channel

Abstract

The subvalent germanium monoxide (GeO, X1Σ+) molecule has been prepared via the elementary reaction of atomic germanium (Ge, 3P j ) and molecular oxygen (O2, X3Σg –) with each reactant in its electronic ground state by means of single-collision conditions. The merging of electronic structure calculations with crossed beam experiments suggests that the formation of germanium monoxide (GeO, X1Σ+) commences on the singlet surface through unimolecular decomposition of a linear singlet collision complex (GeOO, i1, C∞v, 1Σ+) via intersystem crossing (ISC) yielding nearly exclusively germanium monoxide (GeO, X1Σ+) along with atomic oxygen in its electronic ground state [p1, O­(3P)]. These results provide a sophisticated reaction mechanism of the germanium–oxygen system and demonstrate the efficient “heavy atom effect” of germanium in ISC yielding (nearly) exclusive singlet germanium monoxide and triplet atomic oxygen compared to similar systems (carbon dioxide and dinitrogen monoxide), in which non-adiabatic reaction dynamics represent only minor channels.

Spiers Memorial Lecture: New directions in molecular scattering

“…In general, the application of theory in combination with crossed-molecularbeams experiments has led to fundamental understanding of quite complex reactions. [234][235][236][237][238][239][240][241][242][243][244][245][246][247][248][249][250][251] The impact of modern scattering on real systems can be exem-plied in the studies of O( 3 P) + C 6 H 6 (benzene). Here, a theoretical statistical approach could be validated by comparison to the crossed-molecular-beam results and subsequently used to compute channel-specic rate constants as a function of temperature and pressure.…”

Anion Photoelectron Spectroscopy and Theoretical Studies of Ge3n+1O (n = 1–3) Clusters with the C3v Symmetric Ge3 Structural Unit

“…Moreover, the chemical bonding analyses of germanium oxide clusters could provide further insights into the germanium–germanium and germanium–oxygen interactions which in turn are helpful to realize the assemblies of nanostructures. In the last decades, a number of anionic and neutral germanium oxide clusters including GeO, − GeO 2 –/0 , ,− GeO 4 – , Ge 2 O 2 –/0 , ,,, Ge 2 O 3 –/0 , Ge 3 O –/0 , , Ge 3 O 2 – , Ge 3 O 3 –/0 , ,,, Ge 3 O 4 – , Ge 3 O 5 – , Ge 4 O 4 –/0 , ,,, Ge 5 O 5 – , and Ge 6 O –/0 have been investigated using spectroscopic experiments and theoretical calculations.…”

Identification of Ge≡O Triple Bond in Ge6O– Cluster: Anion Photoelectron Spectroscopy and Theoretical Calculations

“…Investigating the structures and chemical bonding of silicon oxide and germanium oxide clusters may provide useful information for the syntheses of novel compounds with unusual chemical bonds such as SiO or GeO triple bonds as well as for their applications in the Si-based or Ge-based field effect transistors, integrated optics devices, and high-capacity Li ion batteries . Many silicon oxide clusters − and germanium oxide clusters − have been investigated experimentally and/or theoretically. The dissociation energies, ionization energies, and vibrational frequencies of SiO ,, and GeO ,,,− have been studied using mass spectroscopy, He­(I) photoelectron spectroscopy, photoionization measurements, and infrared spectroscopy experiments as well as theoretical calculations. , However, the bonding properties of SiO and GeO have not been investigated in detail.…”