The subvalent germanium monoxide (GeO, XΣ) molecule has been prepared via the elementary reaction of atomic germanium (Ge, P) and molecular oxygen (O, XΣ) 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, XΣ) commences on the singlet surface through unimolecular decomposition of a linear singlet collision complex (GeOO, , C, Σ) via intersystem crossing (ISC) yielding nearly exclusively germanium monoxide (GeO, XΣ) along with atomic oxygen in its electronic ground state [, O(P)]. 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.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.jpclett.2c00706 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Experimental and theoretical study of the Sn-O bond formation between atomic tin and molecular oxygen.
Phys Chem Chem Phys
November 2024
Department of Chemistry, University of Hawai'i at Manoa, Honolulu, HI 96822, USA.
The merging of the electronic structure calculations and crossed beam experiments expose the reaction dynamics in the tin (Sn, P) - molecular oxygen (O, XΣ-g) system yielding tin monoxide (SnO, XΣ) along with ground state atomic oxygen O(P). The reaction can be initiated on the triplet and singlet surfaces addition of tin to the oxygen atom leading to linear, bent, and/or triangular reaction intermediates. On both the triplet and singlet surfaces, formation of the tin dioxide structure is required prior to unimolecular decomposition to SnO(XΣ) and O(P).
View Article and Find Full Text PDFGermaborene reactivity study - addition of carbon nucleophiles, cycloaddition reactions, coordination chemistry.
Chem Sci
July 2024
Institut für Anorganische Chemie Auf der Morgenstelle 18 72076 Tübingen Germany
NHC substituted germaborenium cation 2 was synthesized directly in reaction of bromo-substituted germaborene 1b with NHC. The adamantyl isonitrile substituted germaborenium cation 4 was obtained stepwise: substitution of the chloride atom against adamantyl isonitrile at the B-Cl unit in 1a, simultaneous migration of the chloride to the germanium atom followed by chloride abstraction using Na[BAr ] gives the germaborenium cation 4. Substitution of the bromide atom in 1b against carbon monoxide followed by bromide abstraction using Ag[Al(OBu)] leads to compound 6 exhibiting a B[double bond, length as m-dash]C double bond substituted at the boron atom by a germylium cation.
View Article and Find Full Text PDFDisentangling the activity-selectivity trade-off in catalytic conversion of syngas to light olefins.
Science
May 2023
State Key Laboratory of Catalysis, 2011-Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Breaking the trade-off between activity and selectivity has been a long-standing challenge in the field of catalysis. We demonstrate the importance of disentangling the target reaction from the secondary reactions for the case of direct syngas conversion to light olefins by incorporating germanium-substituted AlPO-18 within the framework of the metal oxide-zeolite (OXZEO) catalyst concept. The attenuated strength of the catalytically active Brønsted acid sites allows enhancing the targeted carbon-carbon coupling of ketene intermediates to form olefins by increasing the active site density while inhibiting secondary reactions that consume the olefins.
View Article and Find Full Text PDFCompact Radio Frequency Discharge-Pumped Slab CO Laser System with a Zinc Germanium Phosphide (ZnGeP) Sum-Frequency Generator for Remote Sensing of the Atmosphere.
Appl Spectrosc
December 2022
230759Institute of Monitoring of Climatic and Ecological Systems, Siberian Branch, Russian Academy of Sciences, Tomsk, Russia.
Based on our experimental study of spectral characteristics of an improved compact CO laser system, the prospects of using such a laser system for solving urgent problems of atmospheric sounding were demonstrated. An increase in the number of laser lines due to intracavity generation of the second harmonic and sum-frequencies in a nonlinear zinc germanium phosphide (ZnGeP) crystal enriches capabilities of the laser. It was shown that such a CO laser system with frequency conversion in ZnGeP crystal can be used for detection and measuring concentration of at least 14 minor natural and pollution gases components of the atmosphere.
View Article and Find Full Text PDFGas-Phase Preparation of Subvalent Germanium Monoxide (GeO, X) via Non-Adiabatic Reaction Dynamics in the Exit Channel.
J Phys Chem Lett
May 2022
Department of Chemistry and Biochemistry, Florida International University, Miami, Florida 33199, United States.
The subvalent germanium monoxide (GeO, XΣ) molecule has been prepared via the elementary reaction of atomic germanium (Ge, P) and molecular oxygen (O, XΣ) 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, XΣ) commences on the singlet surface through unimolecular decomposition of a linear singlet collision complex (GeOO, , C, Σ) via intersystem crossing (ISC) yielding nearly exclusively germanium monoxide (GeO, XΣ) along with atomic oxygen in its electronic ground state [, O(P)]. 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.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!