arXiv subjects

Ding Pan

Publications and source records attributed to Ding Pan.

At least 37 records · Page 2Linked to original sources

arXiv2024

Super-concentrated alkali hydroxide electrolytes for rechargeable Zn batteries

Rechargeable Zn batteries offer safe, inexpensive energy storage, but when deeply discharged to compete with lithium-ion batteries, they are plagued by parasitic reactions at the Zn anodes. We apply super-concentrated alkaline electrolytes to suppress two key parasitic reactions, hydrogen evolution and ZnO passivation. An electrolyte with 15 M KOH displays a broad electrochemical window (>2.5 V on Au), a high ZnO solubility (>1.5 M), and an exceptionally high ionic conductivity (>0.27 S/cm at 25 C). Spectroscopies and ab-initio molecular dynamics simulation suggest K+-OH- pairs and a tightened water network to underpin the stability. The simulation further reveals unique triggered proton hopping that offsets the lack of water wires to sustain the conductivity. Low hydrogen evolution, confirmed via online mass spectroscopy, and slow passivation enable a NiOOH||Zn battery to deliver a cumulative capacity of 8.4 Ah cm-2 and a Zn-air battery to last for over 110 hours.

cond-mat.mtrl-sci↗

arXiv2024

Unveiling the hidden reaction kinetic network of carbon dioxide in supercritical aqueous solutions

Dissolution of CO$_2$ in water followed by the subsequent hydrolysis reactions is of great importance to the global carbon cycle, and carbon capture and storage. Despite enormous previous studies, the reactions are still not fully understood at the atomistic scale. Here, we combined ab initio molecular dynamics simulations with Markov state models to elucidate the reaction mechanisms and kinetics of CO$_2$ in supercritical water both in the bulk and nanoconfined states. The integration of unsupervised learning with first-principles data allows us to identify complex reaction coordinates and pathways automatically instead of a priori human speculation. Interestingly, our unbiased modelling found a novel pathway of dissolving CO$_2$(aq) under graphene nanoconfinement, involving the pyrocarbonate anion (C$_2$O$_5^{2-}$(aq)) as an intermediate state. The pyrocarbonate anion was previously hypothesized to have a fleeting existence in water; however our study reveals that it is a crucial reaction intermediate and stable carbon species in the nanoconfined solutions. We even observed the formation of pyrocarbonic acid (H$_2$C$_2$O$_5$(aq)), which was unknown in water. The unexpected appearance of pyrocarbonates is related to the superionic behavior of the confined solutions. We also found that carbonation reactions involve collective proton transfer along transient water wires, which exhibits concerted behavior in the bulk solution but proceeds stepwise under nanoconfinement. Our study highlights the importance of large oxocarbons in aqueous carbon reactions, with great implications for the deep carbon cycle and the sequestration of CO$_2$.

physics.chem-ph↗

arXiv2023

Raman and IR spectra of water under graphene nanoconfinement at ambient and extreme pressure-temperature conditions: a first-principles study

The nanoconfinement of water can result in dramatic differences in its physical and chemical properties compared to bulk water. However, a detailed molecular-level understanding of these properties is still lacking. Vibrational spectroscopy, such as Raman and infrared, is a popular experimental tool for studying the structure and dynamics of water, and is often complemented by atomistic simulations to interpret experimental spectra, but there have been few theoretical spectroscopy studies of nanoconfined water using first-principles methods at ambient conditions, let alone under extreme pressure-temperature conditions. Here, we computed the Raman and IR spectra of water nanoconfined by graphene at ambient and extreme pressure-temperature conditions using ab intio simulations. Our results revealed alterations in the Raman stretching and low-frequency bands due to the graphene confinement. We also found spectroscopic evidence indicating that nanoconfinement considerably changes the tetrahedral hydrogen bond network, which is typically found in bulk water. Furthermore, we observed an unusual bending band in the Raman spectrum at ~10 GPa and 1000 K, which is attributed to the unique molecular structure of confined ionic water. Additionally, we found that at ~20 GPa and 1000 K, confined water transformed into a superionic fluid, making it challenging to identify the IR stretching band. Finally, we computed the ionic conductivity of confined water in the ionic and superionic phases. Our results highlight the efficacy of Raman and IR spectroscopy in studying the structure and dynamics of nanoconfined water in a large pressure-temperature range. Our predicted Raman and IR spectra can serve as a valuable guide for future experiments.

cond-mat.mtrl-sci↗

arXiv2023

Truncated atomic plane wave method for the subband structure calculations of Moiré systems

We propose a highly efficient and accurate numerical scheme named Truncated Atomic Plane Wave (TAPW) method to determine the subband structure of Twisted Bilayer Graphene (TBG) inspired by BM model. Our method utilizes real space information of carbon atoms in the moiré unit cell and projects the full tight binding Hamiltonian into a much smaller subspace using atomic plane waves. We present accurate electronic band structures of TBG in a wide range of twist angles together with detailed moiré potential and screened Coulomb interaction at the first magic angle using our new method. Furthermore, we generalize our formalism to solve the problem of low frequency moiré phonons in TBG.

cond-mat.mes-hall↗

arXiv2022

Probing Deep Speaker Embeddings for Speaker-related Tasks

Deep speaker embeddings have shown promising results in speaker recognition, as well as in other speaker-related tasks. However, some issues are still under explored, for instance, the information encoded in these representations and their influence on downstream tasks. Four deep speaker embeddings are studied in this paper, namely, d-vector, x-vector, ResNetSE-34 and ECAPA-TDNN. Inspired by human voice mechanisms, we explored possibly encoded information from perspectives of identity, contents and channels; Based on this, experiments were conducted on three categories of speaker-related tasks to further explore impacts of different deep embeddings, including discriminative tasks (speaker verification and diarization), guiding tasks (target speaker detection and extraction) and regulating tasks (multi-speaker text-to-speech). Results show that all deep embeddings encoded channel and content information in addition to speaker identity, but the extent could vary and their performance on speaker-related tasks can be tremendously different: ECAPA-TDNN is dominant in discriminative tasks, and d-vector leads the guiding tasks, while regulating task is less sensitive to the choice of speaker representations. These may benefit future research utilizing speaker embeddings.

eess.AS↗

arXiv2022

Highly active hydrogen evolution facilitated by topological surface states on a Pd/SnTe metal/topological crystalline insulator heterostructure

Recently, topological quantum materials have emerged as a promising electrocatalyst for hydrogen evolution reaction (HER). However, most of their performance largely lags behind noble metals such as benchmark platinum (Pt). In this work, a Pd(20nm)/SnTe(70nm) heterostructure, fabricated by molecular beam epitaxy and electron beam evaporation, is found to display much higher electrocatalytic activity than that of a pure Pd(20nm) thin film and even higher than that of a commercial Pt foil. This heterostructure adopts an extracted turnover frequency value more than two times higher than that of the Pd(20nm) thin film at a potential of 0.2 V, indicating a much higher intrinsic activity per Pd site. Density functional theory calculations show that the conventional d-band theory, which works well for many transition metal heterostructures, cannot explain the enhancement of electrocatalytic performance. Instead, we found that the topological surface states (TSSs) of the SnTe (001) underlayer play a key role; electrons transfer from both the Pd surface and the adsorbed H atoms to the TSSs of SnTe (001), resulting in weaker Pd-H binding strength and more favorable hydrogen adsorption free energies. Our work demonstrates for the first time that a metal/topological quantum material heterostructure could be a prominent catalyst to enjoy HER activity outperforming that of a commercial Pt foil and offers a promising direction to optimize the performance of electrocatalysts based on topological quantum materials.

cond-mat.mtrl-sci↗

arXiv2022

Nanoconfinement Facilitates Reactions of Carbon Dioxide in Supercritical Water

The reactions of CO$_2$ in water under extreme pressure-temperature conditions are of great importance to the carbon storage and transport below Earth's surface, which substantially affect the carbon budget in the atmosphere. We applied ab initio molecular dynamics simulations to study aqueous carbon solutions nanoconfined by graphene and stishovite (SiO$_2$) at 10 GPa and 1000$\sim$1400 K. We found that CO$_2$(aq) reacts more in nanoconfinement than in bulk. The stishovite-water interface makes the solutions more acidic, which shifts the chemical equilibria, and the interface chemistry also affects the reaction mechanisms. Our findings suggest that CO$_2$(aq) in deep Earth may be more active than previously thought, and confining CO$_2$ and water in nanopores may enhance the efficiency of mineral carbonation.

physics.chem-ph↗

arXiv2021

Role of topological surface states and mirror symmetry in topological crystalline insulator SnTe as an efficient electrocatalyst

The surface orientation dependence on the hydrogen evolution reaction (HER) performance of topological crystalline insulator (TCI) SnTe thin films is studied. Their intrinsic activities are determined by linear sweep voltammetry and cyclic voltammetry measurements. It is found that SnTe (001) and (111) surfaces exhibit intrinsic activities significantly larger than the (211) surface. Density functional theory calculations reveal that pure (001) and (111) surfaces are not good electrocatalysts, while those with Sn vacancies or partially oxidized surfaces, with the latter as evidenced by X-ray photoelectron spectroscopy, have high activity. The calculated overall performance of the (001) and (111) surfaces with robust topological surface states (TSSs) is better than that of the lowly symmetric (211) surface with fragile or without TSSs, which is further supported by their measured weak antilocalization strength. The high HER activity of SnTe (001) and (111) is attributed to the enhanced charge transfer between H atoms and TSSs. We also address the effect of possible surface facets and the contrast of the HER activity of the available active sites among the three samples. Our study demonstrates that the TSSs and mirror symmetry of TCIs expedite their HER activity.

cond-mat.mtrl-sci↗

arXiv2021

Ab initio molecular dynamics modelling of organic crystal electro-optical properties

Molecular dynamics calculations were preformed on organic crystals 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium tosylate (DAST) and 4-N,N-dimethylamino-4'-N'-methylstilbazolium 2,4,6-trimethylbenzenesulfonate (DSTMS). Vibrational modes of the structures were investigated to examine the single unit cell phononic contribution of the organic crystals to their terahertz generating capabilities. Linear optical properties were also calculated from snapshots of the molecular dynamics structures through Green-Kubo relations, and compared with experimental transmission.

cond-mat.mtrl-sci↗

arXiv2021

Bridging the gap between atomically thin semiconductors and metal leads

Electrically interfacing atomically thin transition metal dichalcogenide semiconductors (TMDSCs) with metal leads is challenging because of undesired interface barriers, which have drastically constrained the electrical performance of TMDSC devices for exploring their unconventional physical properties and realizing potential electronic applications. Here we demonstrate a strategy to achieve nearly barrier-free electrical contacts with few-layer TMDSCs by engineering interfacial bonding distortion. The carrier-injection efficiency of such electrical junction is substantially increased with robust ohmic behaviors from room to cryogenic temperatures. The performance enhancements of TMDSC field-effect transistors are well reflected by the ultralow contact resistance (down to 90 Ohm um in MoS2, towards the quantum limit), the ultrahigh field-effect mobility (up to 358,000 cm2V-1s-1 in WSe2) and the prominent transport characteristics at cryogenic temperatures. This method also offers new possibilities of the local manipulation of structures and electronic properties for TMDSC device design.

cond-mat.mtrl-sci↗

arXiv2021

Raman spectra of hydrocarbons under extreme conditions of pressure and temperature: a first-principles study

Hydrocarbons are of great importance in carbon-bearing fluids in deep Earth and in ice giant planets at extreme pressure (P)-temperature (T) conditions. Raman spectroscopy is a powerful tool to study the chemical speciation of hydrocarbons; however, it is challenging to interpret Raman data at extreme conditions. Here, we performed ab initio molecular dynamics simulations coupled with the modern theory of polarization to calculate Raman spectra of methane, ethane, and propane up to 48 GPa and 2000 K. Our method includes anharmonic temperature effects. We studied the pressure and temperature effects on the Raman bands, and identified the characteristic Raman modes for the C-C and C-C-C bonds. Our result may help to interpret in-situ Raman data of hydrocarbons at extreme P-T conditions, with important implications for understanding the deep carbon cycle inside Earth and the compositions of ice giant planets.

physics.comp-ph↗

arXiv2020

The Lightest 2D Nanomaterial: Freestanding Ultrathin Li Nanosheets by in-situ Electron Microscopy

Lithium (Li) is the simplest metal and the lightest solid element. Here we report the first demonstration of controlled growth of two-dimensional (2D) ultrathin Li nanosheets with large lateral dimensions up to several hundreds of nanometres and thickness limited to just a few nanometres by in-situ transmission electron microscopy (TEM). The nanoscale dynamics of nanosheets growth were unravelled by real-time TEM imaging, which, in combination with density function theory (DFT) calculations indicates that the growth of bcc structured Li into 2D nanosheets is a consequence of kinetic control as mediated by preferential oxidization of the (111) surfaces due to the trace amount of O2 (~10-6 Pa) within TEM chamber. The plasmonic optical properties of the as-grown Li nanosheets were probed by cathodoluminescence (CL) spectroscopy equipped within TEM, and a broadband visible emission was observed that contains contributions of both in-plane and out-of-plane plasmon resonance modes.

physics.chem-ph↗

arXiv2020

Dielectric constant of supercritical water in a large pressure-temperature range

A huge amount of water at supercritical conditions exists in Earth's interior, where its dielectric properties play a critical role in determining how it stores and transports materials. However, it is very challenging to obtain the static dielectric constant of water, $ε_0$, in a wide pressure-temperature (P-T) range as found in deep Earth either experimentally or by first-principles simulations. Here, we introduce a neural network dipole model, which, combined with molecular dynamics, can be used to compute P-T dependent dielectric properties of water as accurately as first-principles methods but much more efficiently. We found that $ε_0$ may vary by one order of magnitude in Earth's upper mantle, suggesting that the solvation properties of water change dramatically at different depths. There is a subtle interplay between the molecular dipole moment and the dipolar angular correlation in governing the change of $ε_0$. We also calculated the frequency-dependent dielectric constant of water in the microwave range, which, to the best of our knowledge, has not been calculated from first principles, and found that temperature affects the dielectric absorption more than pressure. Our results are of great use in many areas, e.g., modelling water-rock interactions in geochemistry. The computational approach introduced here can be readily applied to other molecular fluids.

physics.chem-ph↗

arXiv2019

Expediting hydrogen evolution through topological surface states on Bi2Te3

Recently, the development of efficient and non-noble metal electrocatalysts with excellent durability for the hydrogen evolution reaction (HER) has attracted increasing attention. The exotic and robust metallic surface states of topological insulators (TIs) are theoretically predicted to enhance surface catalytic activity of overlaying catalysts, but no experimental evidence for TIs directly used as electrocatalysts has ever been reported. In this work, we fabricated the TI thin films of Bi2Te3 with different thicknesses using the molecular beam epitaxy method, and found that these thin films exhibit high electrocatalytic activity in HER. The 48 nm Bi2Te3 thin film has the best performance, which is attributed to its largest active area arising from the spiral growth mode of triangular domains as revealed by atomic force microscopy imaging. Importantly, our theoretical calculations reveal that while pure Bi2Te3 is not a good electrocatalyst, the Bi2Te3 thin films with partially oxidized surfaces or Te vacancies have high HER activity. The existence of the corresponding surface oxides on the Bi2Te3 thin films is supported by our X-ray photoelectron spectroscopy data. Particularly, we demonstrate that the topological surface states play a key role in enhancing the HER performance. Our study offers a new direction to design cost-effective electrocatalysts.

physics.chem-ph↗

arXiv2019

Large presence of carbonic acid in CO$_2$-rich aqueous fluids under Earth's mantle conditions

The chemistry of carbon in aqueous fluids at extreme pressure and temperature conditions is of great importance to Earth's deep carbon cycle, which substantially affects the carbon budget at Earth's surface and global climate change. At ambient conditions, the concentration of carbonic acid in water is negligible, so aqueous carbonic acid was simply ignored in previous geochemical models. However, by applying extensive ab initio molecular dynamics simulations at pressure and temperature conditions similar to those in Earth's upper mantle, we found that carbonic acid can be the most abundant carbon species in aqueous CO$_2$ solutions at ~10 GPa and 1000 K. The mole percent of carbonic acid in total dissolved carbon species increases with increasing pressure along an isotherm, while its mole percent decreases with increasing temperature along an isobar. In CO$_2$-rich solutions, we found significant proton transfer between carbonic acid molecules and bicarbonate ions, which may enhance the conductivity of the solutions. The effects of pH buffering by carbonic acid may play an important role in water-rock interactions in Earth's interior. Our findings suggest that carbonic acid is an important carbon carrier in the deep carbon cycle.

physics.chem-ph↗

arXiv2019

Effects of Hexagonal Boron Nitride Encapsulation on the Electronic Structure of Few-layer MoS$_2$

The hexagonal boron nitride (hBN) encapsulation has been widely used in the electronics applications of 2D materials to improve device performance by protecting 2D materials against contamination and degradation. It is often assumed that hBN layers as a dielectric would not affect the electronic structure of encapsulated 2D materials. Here we studied few-layer MoS$_2$ encapsulated in hBN flakes by using a combination of theoretical and experimental Raman spectroscopy. We found that after the encapsulation the out-of-plane A$_{1g}$ mode is upshifted, while the in-plane E$_{2g}^1$ mode is downshifted. The measured downshift of the E$_{2g}^1$ mode does not decrease with increasing the thickness of MoS$_2$, which can be attributed to tensile strains in bilayer and trilayer MoS$_2$ caused by the typical experimental process of the hBN encapsulation. We estimated the strain magnitude and found that the induced strain may cause the K-Q crossover in the conduction band of few-layer MoS$_2$, so greatly modifies its electronic properties as an n-type semiconductor. Our study suggests that the hBN encapsulation should be used with caution, as it may affect the electronic properties of encapsulated few-layer 2D materials.

cond-mat.mtrl-sci↗

arXiv2018

Dielectric properties of condensed systems composed of fragments

The dielectric properties of molecules or nanostructures are usually modified in a complex manner, when assembled into a condensed phase. We propose a first-principles method to compute polarizabilities of sub-entities of solids and liquids, which accounts for multipolar interactions at all orders, and is applicable to any semiconductor or insulator. The method only requires the evaluation of induced fields in the condensed phase, with no need of multiple calculations for each constituent. As an example, we present results for the molecular polarizabilities of water in a wide pressure and temperature range. We found that at ambient conditions, the dipole-induced-dipole approximation is sufficiently accurate and the Clausius-Mossotti relation may be used, e.g. to obtain molecular polarizabilities from experimental refractive indexes. However with increasing pressure this approximation becomes unreliable and in the case of ice X the Clausius-Mossotti relation is not valid.

physics.chem-ph↗

arXiv2016

The fate of carbon dioxide in water-rich fluids at extreme conditions

Investigating the fate of dissolved carbon dioxide under extreme conditions is critical to understanding the deep carbon cycle in the Earth, a process that ultimately influences global climate change. We used first-principles molecular dynamics simulations to study carbonates and carbon dioxide dissolved in water at pressures (P) and temperatures (T) approximating the conditions of the Earth's upper mantle. Contrary to popular geochemical models assuming that molecular CO$_2$(aq) is the major carbon species present in water under deep earth conditions, we found that at 11 GPa and 1000 K carbon exists almost entirely in the forms of solvated carbonate (CO$_3^{2-}$) and bicarbonate (HCO$_3^-$) ions, and that even carbonic acid (H$_2$CO$_3$(aq)) is more abundant than CO$_2$(aq). Furthermore, our simulations revealed that ion pairing between Na$^+$ and CO$_3^{2-}$/HCO$_3^-$ is greatly affected by P-T conditions, decreasing with increasing pressure at 800$\sim$1000 K. Our results suggest that in the Earth's upper mantle, water-rich geo-fluids transport a majority of carbon in the form of rapidly interconverting CO$_3^{2-}$ and HCO$_3^-$ ions, not solvated CO$_2$(aq) molecules.

physics.chem-ph↗