Interaction between CO2 and NbO2+: Infrared photodissociation spectroscopic and theoretical study

Kong, Xiangtao; Shi, Ruili; Wang, Chong; Zheng, Huijun; Wang, Tiantong; Liang, Xiaoqing; Yang, Jianpeng; Jing, Qiangshan; Liu, Yanming; Han, Haiyan; Zhao, Zijian; Fan, Hongjun; Li, Gang; Xie, Hua

doi:10.1016/j.chemphys.2020.110755

Cited by 12 publications

(12 citation statements)

References 42 publications

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“…In contrast, the CO 2 molecule was only weakly bound to the metal cations, exclusively in an end-on configuration via electrostatic charge-quadrupole interaction, resulting in a linear M + OCO structure. − The antisymmetric CO 2 stretching vibrations in these cationic complexes are generally blue-shifted with respect to the free CO 2 molecule. − It was found that these blue-shifted vibrations vary only slightly from one system to another due to electrostatic interaction. − Here we report the generation of the cationic metal complex BeOCO + , which exhibits an antisymmetric CO 2 stretching mode at 2418.9 cm –1 in solid neon, blue-shifted by 71 cm –1 with respect to free CO 2 . The observed value is the highest antisymmetric CO 2 stretching frequency ever reported for a carbon dioxide complex. − …”

Section: Introductionmentioning

confidence: 83%

Covalent Bonding Between Be⁺and CO₂in BeOCO⁺with a Surprisingly High Antisymmetric OCO Stretching Vibration

et al. 2021

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The cationic complex BeOCO+ is produced in a solid neon matrix. Infrared absorption spectroscopic study shows that it has a very high antisymmetric OCO stretching vibration of 2418.9 cm–1, which is about 71 cm–1 blue-shifted from that of free CO2. The quantum chemical calculations are in very good agreement with the experimental observation. Depending on the theoretical method, a linear or quasi-linear structure is predicted for the cation. The analysis of the electronic structure shows that the bonding of Be+ to one oxygen atom induces very little charge migration between the two moieties, but it causes a significant change in the σ-charge distribution that strengthens the terminal C–O bond, leading to the observed blue shift. The bonding analysis reveals that the Be+ ← OCO donation results in strong binding due to the interference of the wave function and a charge polarization within the CO2 fragment and hybridization to Be+ but only negligible charge donation.

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Section: Introductionmentioning

confidence: 83%

Covalent Bonding Between Be⁺and CO₂in BeOCO⁺with a Surprisingly High Antisymmetric OCO Stretching Vibration

et al. 2021

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“… 40 , 42 CO 2 activation has further been studied, for example, on hydrogenated metals, 43 − 45 metal carbide clusters, 46 , 47 and metal oxide species, 29 , 48 − 51 including niobium oxides. 16 , 31 , 52 , 53 In contrast to activation by pure metallic clusters, where carbonyl (CO) formation is observed, activation by metal oxides can lead to the formation of a carbonate radical anion moiety, [CO 3 ] − . 30 , 54 …”

Section: Introductionmentioning

confidence: 99%

Carbon Dioxide and Water Activation by Niobium Trioxide Anions in the Gas Phase

et al. 2023

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Transition metals are important in various industrial applications including catalysis. Due to the current concentration of CO 2 in the atmosphere, various ways for its capture and utilization are investigated. Here, we study the activation of CO 2 and H 2 O at [NbO 3 ] − in the gas phase using a combination of infrared multiple photon dissociation spectroscopy and density functional theory calculations. In the experiments, Fourier-transform ion cyclotron resonance mass spectrometry is combined with tunable IR laser light provided by the intracavity free-electron laser FELICE or optical parametric oscillator-based table-top laser systems. We present spectra of [NbO 3 ] − , [NbO 2 (OH) 2 ] − , [NbO 2 (OH) 2 ] − (H 2 O) and [NbO(OH) 2 (CO 3 )] − in the 240–4000 cm –1 range. The measured spectra and observed dissociation channels together with quantum chemical calculations confirm that upon interaction with a water molecule, [NbO 3 ] − is transformed to [NbO 2 (OH) 2 ] − via a barrierless reaction. Reaction of this product with CO 2 leads to [NbO(OH) 2 (CO 3 )] − with the formation of a [CO 3 ] moiety.

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“…Transformation of carbon dioxide into valued chemicals has received increasing attention in the past few decades. , The coordination and activation of carbon dioxide by transition metal centers are considered as key steps in the catalytic transformation of the extremely thermodynamically stable carbon dioxide into useful organic substances. − The interactions of metal atoms and ions with carbon dioxide may serve as a simple model for understanding the catalytic mechanism and have been intensively studied experimentally either in the gas phase or in solid noble gas matrices. − Spectroscopic studies indicate that carbon dioxide forms various complexes with transition metals in different coordination modes, including η 1 -O end-on, η 1 -C, η 2 -C, O, and η 2 -O, O (Scheme ). − …”

Section: Introductionmentioning

confidence: 99%

Carbon Dioxide Activation by Alkaline-Earth Metals: Formation and Spectroscopic Characterization of OCMCO₃ and MC₂O₄ (M = Ca, Sr, Ba) in Solid Neon

Dong

Wang

et al. 2022

J. Phys. Chem. A

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The reactions of alkaline-earth metal atoms (Ca, Sr, and Ba) with carbon dioxide are investigated using matrix isolation infrared spectroscopy in solid neon. The ground-state metal atoms react with two carbon dioxide molecules to produce the oxalate complexes MC 2 O 4 and the carbonate−carbonyl complexes OCMCO 3 (M = Ca, Sr, Ba) spontaneously on annealing. The species are identified by the effects of isotopic substitution on their infrared spectra as well as density functional calculations. Bonding analyses reveal that the attractive forces between M 2+ and (CO 3 ) 2− or (C 2 O 4 ) 2 − in the OCMCO 3 and MC 2 O 4 complexes come mainly from electrostatic attraction, but covalent orbital interactions also play an important role, which are dominated by the ligand-to-metal donation bonding. The calcium, strontium, and barium metal centers in these complexes use their ns and predominately (n − 1)d atomic orbitals for covalent bonding that mimic transition metals.

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Interaction between CO2 and NbO2+: Infrared photodissociation spectroscopic and theoretical study

Cited by 12 publications

References 42 publications

Covalent Bonding Between Be⁺and CO₂in BeOCO⁺with a Surprisingly High Antisymmetric OCO Stretching Vibration

Covalent Bonding Between Be⁺and CO₂in BeOCO⁺with a Surprisingly High Antisymmetric OCO Stretching Vibration

Carbon Dioxide and Water Activation by Niobium Trioxide Anions in the Gas Phase

Carbon Dioxide Activation by Alkaline-Earth Metals: Formation and Spectroscopic Characterization of OCMCO₃ and MC₂O₄ (M = Ca, Sr, Ba) in Solid Neon

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Interaction between CO2 and NbO2+: Infrared photodissociation spectroscopic and theoretical study

Cited by 12 publications

References 42 publications

Covalent Bonding Between Be+and CO2in BeOCO+with a Surprisingly High Antisymmetric OCO Stretching Vibration

Covalent Bonding Between Be+and CO2in BeOCO+with a Surprisingly High Antisymmetric OCO Stretching Vibration

Carbon Dioxide and Water Activation by Niobium Trioxide Anions in the Gas Phase

Carbon Dioxide Activation by Alkaline-Earth Metals: Formation and Spectroscopic Characterization of OCMCO3 and MC2O4 (M = Ca, Sr, Ba) in Solid Neon

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Covalent Bonding Between Be⁺and CO₂in BeOCO⁺with a Surprisingly High Antisymmetric OCO Stretching Vibration

Covalent Bonding Between Be⁺and CO₂in BeOCO⁺with a Surprisingly High Antisymmetric OCO Stretching Vibration

Carbon Dioxide Activation by Alkaline-Earth Metals: Formation and Spectroscopic Characterization of OCMCO₃ and MC₂O₄ (M = Ca, Sr, Ba) in Solid Neon