Vibrational heavy atom effect controls relaxation and spectral diffusion in triphenyl hydride complexes

Pyles, Cynthia G.; Olson, Courtney M.; Massari, Aaron M.

doi:10.1016/j.chemphys.2018.02.012

Cited by 5 publications

(3 citation statements)

References 36 publications

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“…However, all of the peaks from the EDTA molecule shift toward the low-frequency direction but characteristic peaks of SnO 2 shift to the high-frequency region. We speculate that it is the result of the mass effect, which originates from the binding of heavier Sn and O atoms with the EDTA molecule. , It is worth noting that the asymmetrical stretching and stretching vibration of −NH 2 appear at 3395 and 3203 cm –1 , and the amide III bonds (1256 cm –1 ), which is the C–N bond in the OC–N structure, emerges from the SEAC powder, indicating the formation of primary amide groups in the SEAC powder . Based on the above FTIR results, we consider the EDTA molecule to combine with SnO 2 nanoparticles, and then the terminal −COOH groups are transformed into primary amide groups after introducing the ammonia aqueous solution.…”

Section: Resultsmentioning

confidence: 82%

Tailoring the Energy Band Structure and Interfacial Morphology of the ETL via Controllable Nanocluster Size Achieves High-Performance Planar Perovskite Solar Cells

Wang

Sang

Jiang

et al. 2021

ACS Appl. Mater. Interfaces

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Planar-type perovskite solar cells (p-PSCs) based on SnO 2 have garnered further attention due to their simple and lowtemperature fabrication. Improving the critical properties of the electron transport layer (ETL) is an effective way to enhance the performance of p-PSC devices. Here, a brand-new method is developed to relieve the contact recombination caused by the rough fluorine-doped tin oxide (FTO) surface and further boosts the electrical concentration of the ETL. A SnO 2 −ethylene diamine tetraacetic acid (EDTA) acylamide compound (SEAC) with hydrogen bond-induced adjustable cluster size is reported for the first time. The rational choice of the SEAC cluster size is the key for obtaining the smooth interfacial morphology of the ETL on the rugged FTO substrate. In addition, the energy band gap decreases with the increasing cluster size, and consequently, results in improved electrical conductivity of the SEAC. The upshifted Fermi energy level leads to higher electron concentration, which is an important physical quantity of the ETL. The PSC devices based on the optimized SEAC achieve an improved power conversion efficiency of 21.29% with negligible J−V hysteresis due to significantly enhanced electron transport and reduced contact charge recombination at the ETL/perovskite interface. In general, this paper comes up with a unique strategy to improve the quality of the SnO 2 -based ETL.

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Section: Resultsmentioning

confidence: 82%

Tailoring the Energy Band Structure and Interfacial Morphology of the ETL via Controllable Nanocluster Size Achieves High-Performance Planar Perovskite Solar Cells

Wang

Sang

Jiang

et al. 2021

ACS Appl. Mater. Interfaces

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“…As shown in Figure b, as the temperature increased from 20 to 150 °C, the peak within the range of 3000–3500 cm –1 , arising from the stretching vibration of −OH, was intensified accordingly and shifted to lower wavenumbers. , These results aligned with the generation of Sn–OH species on the Sn surface at elevated temperatures. , The peak at ca. 1840 cm –1 indicated the presence of a Sn–H structure (Figure c), which formed at temperatures exceeding 70 °C. This suggested the dissociation of a water molecule on the Sn surface at elevated temperatures, leading to the formation of a H–Sn···O–H structure, which is similar to our previous research involving the interaction of Zn with hot water .…”

Section: Resultsmentioning

confidence: 99%

“…43,44 The peak at ca. 1840 cm −1 indicated the presence of a Sn−H structure (Figure 4c), 45 which formed at temperatures exceeding 70 °C. This suggested the dissociation of a water molecule on the Sn surface at elevated temperatures, leading to the formation of a H−Sn•••O−H structure, which is similar to our previous research involving the interaction of Zn with hot water.…”

Section: Possible Reaction Pathway Of the Sn-catalyzed Tebrmentioning

confidence: 99%

Thermo-Electrochemically Induced Dynamic Sn^δ+/Sn Interface for Direct Bicarbonate Reduction to Formate

Pei,

Gu,

Cheng

et al. 2023

ACS Catal.

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In traditional electrochemical CO2 reduction (ECR), pressurized pure CO2 gas is typically employed as the feedstock, which consumes large amounts of energy to capture and separate. Herein, we present a method for the direct bicarbonate reduction to formate on a cost-effective Sn foil electrode by integrating the thermochemical and electrochemical methods. Through the simultaneous thermal and electrochemical reactions on the Sn surface, a continuous Snδ+/Sn redox loop was formed. This dynamic Snδ+/Sn interface significantly boosts the direct reduction of bicarbonate to formate, resulting in an optimal partial current density of 121 mA cm–2 for formate with an 83% Faradaic efficiency obtained in 3 mol L–1 KHCO3 at 100 °C. A detailed study revealed that the formate was produced from the bicarbonate directly rather than from the CO2 generated from the dissociation of bicarbonate at elevated temperatures. Compared to the traditional ECR, which involves the complicated processes of CO2 separation, compression, and recirculation, this research presents a straightforward and efficient way for direct bicarbonate reduction, holding promise for practical applications.

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A phase diagram for energy flow-limited reactivity

Zhang

Sibert

Gruebele

2021

The Journal of Chemical Physics

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Intramolecular energy flow (also known as intramolecular vibrational redistribution or IVR) is often assumed in Rice–Ramsperger–Kassel–Marcus, transition state, collisional energy transfer, and other rate calculations not to be an impediment to reaction. In contrast, experimental spectroscopy, computational results, and models based on Anderson localization have shown that ergodicity is achieved rather slowly during molecular energy flow. The statistical assumption in rate theories might easily fail due to quantum localization. Here, we develop a simple model for the interplay of IVR and energy transfer and simulate the model with near-exact quantum dynamics for a 10-degree of freedom system composed of two five-mode molecular fragments. The calculations are facilitated by applying the van Vleck transformation to local random matrix models of the vibrational Hamiltonian. We find that there is a rather sharp “phase transition” as a function of molecular anharmonicity “ a” between a region of facile energy transfer and a region limited by IVR and incomplete accessibility of the state space (classically, the phase space). The very narrow transition range of the order parameter a happens to lie right in the middle of the range expected for molecular torsion, bending, and stretching vibrations, thus demonstrating that reactive energy transfer dynamics several k B T above the thermal energy occurs not far from the localization boundary, with implications for controllability of reactions.

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Vibrational heavy atom effect controls relaxation and spectral diffusion in triphenyl hydride complexes

Cited by 5 publications

References 36 publications

Tailoring the Energy Band Structure and Interfacial Morphology of the ETL via Controllable Nanocluster Size Achieves High-Performance Planar Perovskite Solar Cells

Tailoring the Energy Band Structure and Interfacial Morphology of the ETL via Controllable Nanocluster Size Achieves High-Performance Planar Perovskite Solar Cells

Thermo-Electrochemically Induced Dynamic Sn^δ+/Sn Interface for Direct Bicarbonate Reduction to Formate

A phase diagram for energy flow-limited reactivity

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Vibrational heavy atom effect controls relaxation and spectral diffusion in triphenyl hydride complexes

Cited by 5 publications

References 36 publications

Tailoring the Energy Band Structure and Interfacial Morphology of the ETL via Controllable Nanocluster Size Achieves High-Performance Planar Perovskite Solar Cells

Tailoring the Energy Band Structure and Interfacial Morphology of the ETL via Controllable Nanocluster Size Achieves High-Performance Planar Perovskite Solar Cells

Thermo-Electrochemically Induced Dynamic Snδ+/Sn Interface for Direct Bicarbonate Reduction to Formate

A phase diagram for energy flow-limited reactivity

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Product

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About

Thermo-Electrochemically Induced Dynamic Sn^δ+/Sn Interface for Direct Bicarbonate Reduction to Formate