TY - JOUR
T1 - Gas-Phase Preparation of Subvalent Germanium Monoxide (GeO, X1ς +) via Non-Adiabatic Reaction Dynamics in the Exit Channel
AU - He, Chao
AU - Goettl, Shane J.
AU - Yang, Zhenghai
AU - Kaiser, Ralf I.
AU - Nikolayev, Anatoliy A.
AU - Azyazov, Valeriy N.
AU - Mebel, Alexander M.
N1 - Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/5/26
Y1 - 2022/5/26
N2 - The subvalent germanium monoxide (GeO, X1ς+) molecule has been prepared via the elementary reaction of atomic germanium (Ge, 3Pj) 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∞v1ς+) 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.
AB - The subvalent germanium monoxide (GeO, X1ς+) molecule has been prepared via the elementary reaction of atomic germanium (Ge, 3Pj) 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∞v1ς+) 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.
UR - https://www.scopus.com/pages/publications/85131105658
U2 - 10.1021/acs.jpclett.2c00706
DO - 10.1021/acs.jpclett.2c00706
M3 - 文章
C2 - 35584300
AN - SCOPUS:85131105658
SN - 1948-7185
VL - 13
SP - 4589
EP - 4597
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 20
ER -