arXiv subjects

Jun-Rong Zhang

Publications and source records attributed to Jun-Rong Zhang.

5 recordsLinked to original sources

arXiv2026

Core-Level Spectroscopy Decodes Bond-Alternation Dynamics of Cyclo[18]Carbon

The advent of X-ray free-electron lasers and high-harmonic generation has made time-resolved X-ray spectroscopy a powerful tool for probing local atomic environments, yet whether localized core excitations can report on global collective distortions remains open. Cyclo[18]carbon (C$_{18}$), with its polyynic ground state (D$_\text{9h}$) and cumulenic transition state (D$_\text{18h}$), provides an ideal model to address this long-standing issue in bond-length alternation (BLA) dynamics. Mapping two-dimensional potential energy surfaces by first-principles simulations, we find that core ionization symmetrizes the ground-state double-well potential along the BLA coordinate. Our calculated X-ray spectra reveal remarkable sensitivity to bond-length variations: C1s ionization potentials vary by up to 2.4~eV across the BLA coordinate (1.1--1.4~\AA), with a 0.9~eV variation for minima predicted by different functionals, while NEXAFS $\pi^*$ peaks shift by up to 4~eV across the same coordinate. These predicted signatures provide a quantitative spectroscopy--structure dictionary for decoding transient structures in future ultrafast X-ray experiments and monitoring bond-alternation dynamics in real time.

physics.atm-clus↗

arXiv2025

Mapping Transient Structures of Cyclo[18]Carbon by Computational X-Ray Spectra

The structure of cyclo[18]carbon (C$_{18}$), whether in its polyynic form with bond length alternation (BLA) or its cumulenic form without BLA, has long fascinated researchers, even prior to its successful synthesis. Recent studies suggest a polyynic ground state and a cumulenic transient state; however, the dynamics remain unclear and lack experimental validation. This study presents a first-principles theoretical investigation of the bond lengths ($R_1$ and $R_2$) dependent two-dimensional potential energy surfaces (PESs) of C$_{18}$, concentrating on the ground state and carbon 1s ionized and excited states. We examine the potential of X-ray spectra for determining bond lengths and monitoring transient structures, finding that both X-ray photoelectron (XPS) and absorption (XAS) spectra are sensitive to these variations. Utilizing a library of ground-state minimum structures optimized with 14 different functionals, we observe that core binding energies predicted with the $\omega$B97XD functional can vary by 0.9 eV (290.3--291.2 eV). Unlike the ground state PES, which predicts minima at alternating bond lengths, the C1s ionized state PES predicts minima with equivalent bond lengths. In the XAS spectra, peaks 1$\pi^*$ and 2$\pi^*$ show a redshift with increasing bond lengths along the line where $R_1 = R_2$. Additionally, increasing $R_2$ (with $R_1$ fixed) results in an initial redshift followed by a blueshift, minimizing at $R_1 = R_2$. Major peaks indicate that both 1$\pi^*$ and 2$\pi^*$ arise from two channels: C1s$\rightarrow\pi^*_{z}$ (out-of-plane) and C1s$\rightarrow\pi^*_{xy}$ (in-plane) transitions at coinciding energies.

physics.chem-ph↗

arXiv2024

Effects of Structural Variations to X-ray Absorption Spectra of g-C$_3$N$_4$: Insights from DFT and TDDFT Simulations

X-ray absorption spectroscopy (XAS) is widely employed for structure characterization of graphitic carbon nitride (g-C$_3$N$_4$) and its composites. Nevertheless, even for pure g-C$_3$N$_4$, discrepancies in energy and profile exist across different experiments, which can be attributed to variations in structures arising from diverse synthesis conditions and calibration procedures. Here, we conducted a theoretical investigation on XAS of three representative g-C$_3$N$_4$ structures (planar, corrugated, and micro-corrugated) optimized with different strategies, to understand the structure-spectroscopy relation. Different methods were compared, including density functional theory (DFT) with the full (FCH) or equivalent (ECH) core-hole approximation, as well as the time-dependent DFT (TDDFT). FCH was responsible for getting accurate absolute absorption energy; while ECH and TDDFT aided in interpreting the spectra, through ECH-state canonical molecular orbitals (ECH-CMOs) and natural transition orbitals (NTOs), respectively. With each method, the spectra at the three structures show evident differences, which can be correlated to different individual experiments or in between. Our calculations explained the structural reason behind the spectral discrepancies among different experiments. Moreover, profiles predicted by these methods also displayed consistency, so their differences can be used as a reliable indicator of their accuracy. Both ECH-CMOs and NTO particle orbitals led to similar graphics, validating their applicability in interpreting the transitions. This work provides a comprehensive analysis of the structure-XAS relation for g-C$_3$N$_4$, provides concrete explanations for the spectral differences reported in various experiments, and offers insight for future structure dynamical and transient X-ray spectral analyses.

cond-mat.mtrl-sci↗

arXiv2023

Global Impact and Balancing Act: Deciphering the Effect of Fluorination on B1s Binding Energies in Fluorinated $h$-BN Nanosheets

X-ray photoelectron spectroscopy (XPS) is an important characterization tool in the pursuit of controllable fluorination of two-dimensional hexagonal boron nitride ($h$-BN). However, there is a lack of clear spectral interpretation and seemingly conflicting measurements exist. To discern the structure-spectroscopy relation, we performed a comprehensive first-principles study on the boron 1s edge XPS of fluorinated $h$-BN (F-BN) nanosheets. By gradually introducing 1--6 fluorine atoms into different boron or nitrogen sites, we created various F-BN structures with doping ratios ranging from 1-6\%. Our calculations reveal that fluorines landed at boron or nitrogen sites exert competitive effects on the B1s binding energies (BEs), leading to red or blue shifts in different measurements. Our calculations affirmed the hypothesis that fluorination affects 1s BEs of all borons in the $\pi$-conjugated system, undermining the transferability from $h$-BN to F-BN. Additionally, we observe that BE generally increases with higher fluorine concentration when both borons and nitrogens are non-exclusively fluorinated. These findings provide critical insights into how fluorination affects boron's 1s BEs, contributing to a better understanding of fluorination functionalization processes in $h$-BN and its potential applications in materials science.

cond-mat.mtrl-sci↗

arXiv2020

Topological Superconductivity in Rashba Spin-Orbital Coupling Suppressed Monolayer \{beta}-Bi2Pd

The weak interlayer Van Der Waals material \{beta}-Bi2Pd has recently been established as a strong topological superconductor candidate with unconventional spin-triplet pairing and Majorana zero modes at vortices. In this letter, we study the topological characters and the superconducting pairing, which are still obscure in monolayer \{beta}-Bi2Pd, in light of our effective theoretical model. We find that the non-Rashba spin-orbital coupling plays a critical role in realizing and tuning various novel topological natures. In particular, the spin-triplet p-wave superconducting pairing with Majorana zero mode is revealed in monolayer \{beta}-Bi2Pd. Our studies deepen the understanding of topology and superconductivity in monolayer \{beta}-Bi2Pd and indicate it is a promising platform for achieving low-dimentional topological superconductivity.

cond-mat.mes-hall↗