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The proliferation of large language models (LLMs) has significantly enhanced text generation capabilities across various industries. However, these models' ability to generate human-like text poses substantial challenges in discerning between human and AI authorship. Despite the effectiveness of existing AI-generated text detectors, their development is hindered by the lack of comprehensive, publicly available benchmarks. Current benchmarks are limited to specific scenarios, such as question answering and text polishing, and predominantly focus on English texts, failing to capture the diverse applications and linguistic nuances of LLMs. To address these limitations, this paper constructs a comprehensive bilingual benchmark in both Chinese and English to evaluate mainstream AI-generated text detectors. We categorize LLM text generation into five distinct operations: Create, Update, Delete, Rewrite, and Translate (CUDRT), encompassing all current LLMs activities. We also establish a robust benchmark evaluation framework to support scalable and reproducible experiments. For each CUDRT category, we have developed extensive datasets to thoroughly assess detector performance. By employing the latest mainstream LLMs specific to each language, our datasets provide a thorough evaluation environment. Extensive experimental results offer critical insights for optimizing AI-generated text detectors and suggest future research directions to improve detection accuracy and generalizability across various scenarios., Comment: 32 pages

We show empirically that a phase-space non-Born-Oppenheimer electronic Hamiltonian approach to quantum chemistry (where the electronic Hamiltonian is parameterized by both nuclear position and momentum, (H(R,P)) is both a practical and accurate means to recover vibrational circular dichroism spectra. We further hypothesize that such a phase space approach may lead to very new dynamical physics beyond spectroscopy circular dichroism, with potential implications for understanding chiral induced spin selectivity (CISS), noting that classical phase space approaches conserve the total nuclear plus electronic momentum, whereas classical Born-Oppenheimer approaches do not (they conserve only the nuclear momentum), Comment: 46 pages, 5 figures

In recent years, generative artificial intelligence models, represented by Large Language Models (LLMs) and Diffusion Models (DMs), have revolutionized content production methods. These artificial intelligence-generated content (AIGC) have become deeply embedded in various aspects of daily life and work. However, these technologies have also led to the emergence of Fake Artificial Intelligence Generated Content (FAIGC), posing new challenges in distinguishing genuine information. It is crucial to recognize that AIGC technology is akin to a double-edged sword; its potent generative capabilities, while beneficial, also pose risks for the creation and dissemination of FAIGC. In this survey, We propose a new taxonomy that provides a more comprehensive breakdown of the space of FAIGC methods today. Next, we explore the modalities and generative technologies of FAIGC. We introduce FAIGC detection methods and summarize the related benchmark from various perspectives. Finally, we discuss outstanding challenges and promising areas for future research.

Noncentrosymmetric magnets usually host intriguing magnetic interactions inherent the crystal structure with broken inversion symmetry, which can give rise to rich magnetic behaviors. We report herein the high-pressure synthesis, crystal structure, magnetizations and magnetic structure of a so-called Nowotny chimney ladder compound Cr4Ge7. Our analysis on the powder neutron diffraction data revises the crystal structure as a noncentrosymmetric space group (P-4c2, No.116). It exhibits two magnetic orders within the temperature range of 2 - 400 K. The first order at ~ 207 K associated with a small magnetic moment of ~ 0.75 miuB is assigned to a commensurate ferromagnetic structure with a propagation vector k = (0, 0, 0). The weak itinerant ferromagnet nature should be caused by the complex Cr spin orders from different Wyckoff positions. The second order at ~ 18 K is assumed to arise from a competition between the Dzyaloshinskii-Moria and Heisenberg interactions. The results provide an excellent platform for study on intricate interactions between various magnetic exchanges as well as for the exploration of high temperature exotic magnetic properties which host potential applications in next-generation spintronics., Comment: 21 pages, 5 figures, 2 tables; Supporting Information is not included

Privacy policies have emerged as the predominant approach to conveying privacy notices to mobile application users. In an effort to enhance both readability and user engagement, the concept of contextual privacy policies (CPPs) has been proposed by researchers. The aim of CPPs is to fragment privacy policies into concise snippets, displaying them only within the corresponding contexts within the application's graphical user interfaces (GUIs). In this paper, we first formulate CPP in mobile application scenario, and then present a novel multimodal framework, named SeePrivacy, specifically designed to automatically generate CPPs for mobile applications. This method uniquely integrates vision-based GUI understanding with privacy policy analysis, achieving 0.88 precision and 0.90 recall to detect contexts, as well as 0.98 precision and 0.96 recall in extracting corresponding policy segments. A human evaluation shows that 77% of the extracted privacy policy segments were perceived as well-aligned with the detected contexts. These findings suggest that SeePrivacy could serve as a significant tool for bolstering user interaction with, and understanding of, privacy policies. Furthermore, our solution has the potential to make privacy notices more accessible and inclusive, thus appealing to a broader demographic. A demonstration of our work can be accessed at https://cpp4app.github.io/SeePrivacy/, Comment: USENIX Security 2024. arXiv admin note: text overlap with arXiv:2307.01691

Modern electronic structure theory is built around the Born-Oppenheimer approximation and the construction of an electronic Hamiltonian H_{el}(X) that depends on the nuclear position X (and not the nuclear momentum P). In this article, using the well-known theory of electron translation (Gamma') and rotational (Gamma'') factors to couple electronic transitions to nuclear motion, we construct a practical phase-space electronic Hamiltonian that depends on both nuclear position and momentum, H_{PS}(X,P). While classical Born-Oppenheimer dynamics that run along the eigensurfaces of the operator H_{el}(X) can recover many nuclear properties correctly, we present some evidence that motion along the eigensurfaces of H_{PS}(X,P) can better capture both nuclear and electronic properties (including the elusive electronic momentum studied by Nafie). Moreover, only the latter (as opposed to the former) conserves the total linear and angular momentum in general.

Within the context of FSSH dynamics, one often wishes to remove the angular component of the derivative coupling between states $\left|J\right>$ and $\left|K\right>$. In a set of previous papers, Truhlar {\em et al.} posited one approach for such a removal based on direct projection, while we isolated a second approach by constructing and differentiating rotationally invariant basis. Unfortunately, neither approach was able to demonstrate a {\em one-electron operator} $\hat{O}$ whose matrix element $\left$ was the angular component of the derivative coupling. Here, we show that a one-electron operator can in fact be constructed efficiently in a semi-local fashion. The present results yield physical insight into designing new surface hopping algorithms and be of immediate use for FSSH calculations.

Text style transfer is increasingly prominent in online entertainment and social media. However, existing research mainly concentrates on style transfer within individual English sentences, while ignoring the complexity of long Chinese texts, which limits the wider applicability of style transfer in digital media realm. To bridge this gap, we propose a Chinese Article-style Transfer framework (CAT-LLM), leveraging the capabilities of Large Language Models (LLMs). CAT-LLM incorporates a bespoke, pluggable Text Style Definition (TSD) module aimed at comprehensively analyzing text features in articles, prompting LLMs to efficiently transfer Chinese article-style. The TSD module integrates a series of machine learning algorithms to analyze article-style from both words and sentences levels, thereby aiding LLMs thoroughly grasp the target style without compromising the integrity of the original text. In addition, this module supports dynamic expansion of internal style trees, showcasing robust compatibility and allowing flexible optimization in subsequent research. Moreover, we select five Chinese articles with distinct styles and create five parallel datasets using ChatGPT, enhancing the models' performance evaluation accuracy and establishing a novel paradigm for evaluating subsequent research on article-style transfer. Extensive experimental results affirm that CAT-LLM outperforms current research in terms of transfer accuracy and content preservation, and has remarkable applicability to various types of LLMs., Comment: 9 pages

Since the commencement of the first SETI observation in 2019, China's Search for Extraterrestrial Intelligence program has garnered momentum through domestic support and international collaborations. Several observations targeting exoplanets and nearby stars have been conducted with the FAST. In 2023, the introduction of the Far Neighbour Project(FNP) marks a substantial leap forward, driven by the remarkable sensitivity of the FAST telescope and some of the novel observational techniques. The FNP seeks to methodically detect technosignatures from celestial bodies, including nearby stars, exoplanetary systems, Milky Way globular clusters, and more. This paper provides an overview of the progress achieved by SETI in China and offers insights into the distinct phases comprising the FNP. Additionally, it underscores the significance of this project's advancement and its potential contributions to the field., Comment: Submitted for publication in Journal of Physics: Conference Series (HAPP 10th Anniversary Commemorative Volume). Invited talk online discussion panel on "Searching for Extraterrestrial Intelligence Over a Century" at the Centre for the History and Philosophy of Physics (HAPP) at the University of Oxford on Saturday 27th November 2021

The occurrence of charge-density-wave (CDW) order is a common thread in the phase diagram of cuprate high-transition-temperature ($T_c$) superconductors. In iron-based superconductors (FeSCs), nematic order and fluctuations play a decisive role in driving other emergent orders. CDW order has been observed by scanning tunneling microscopy for various FeSCs such as FeSe thin films, uniaxially strained LiFeAs, and tetragonal FeSe$_{0.81}$S$_{0.19}$. However, it remains elusive if the CDW in these materials is a bulk phenomenon as well as if and how it intertwines with the electronic nematicity. Using energy-resolved resonant X-ray scattering at the Fe-L$_3$ edge, we report the discovery of a local-strain-induced incommensurate isotropic CDW order in FeSe$_{0.82}$S$_{0.18}$. A highly anisotropic CDW response under uniaxial strain unambiguously manifests that the CDW is directly coupled to the nematicity. Transforming part of Fe$^{2+}$ to Fe$^{3+}$ on the surface of FeSe$_{1-x}$S$_{x}$ reveals that the same isotropic CDW can be induced, enhanced, and stabilized in the whole nematic regime measured ($x=0-0.19$). As Fe$^{3+}$ can create local lattice distortions on the surface, the CDW could arise from the interaction between the local strain around Fe$^{3+}$ and the nematic electron correlations. Our experimental observation of a local-strain-induced CDW gives vital information for understanding the interplay between electron correlations and the electronic nematicity in FeSCs., Comment: 7 pages, 4 figures

We show that standard Ehrenfest dynamics does not conserve linear and angular momentum when using a basis of truncated adiabatic states. However, we also show that previously proposed effective Ehrenfest equations of motion[Amano2005,Krishna2007] involving the non-Abelian Berry force do maintain momentum conservation. As a numerical example, we investigate the Kramers' doublet of the methoxy radical using generalized Hartree-Fock with spin-orbit coupling and confirm angular momentum is conserved with the proper equations of motion. Our work makes clear some of the limitations of the Born-Oppenheimer approximation when using ab initio electronic structure theory to treat systems with unpaired electronic spin degrees of freedom and we demonstrate that Ehrenfest dynamics can offer much improved, qualitatively correct results.

Search for extraterrestrial intelligence (SETI) has been mainly focused on nearby stars and their planets in recent years. Barnard's star is the second closest star system to the sun and the closest star in the FAST observable sky which makes the minimum Equivalent Isotropic Radiated Power (EIRP) required for a hypothetical radio transmitter from Barnard's star to be detected by FAST telescope a mere 4.36x10^8 W. In this paper, we present the Five-hundred-meter Aperture Spherical radio Telescope (FAST) telescope as the most sensitive instrument for radio SETI observations toward nearby star systems and conduct a series of observations to Barnard's star (GJ 699). By applying the multi-beam coincidence matching (MBCM) strategy on the FAST telescope, we search for narrow-band signals (~Hz) in the frequency range of 1.05-1.45 GHz, and two orthogonal linear polarization directions are recorded. Despite finding no evidence of radio technosignatures in our series of observations, we have developed predictions regarding the hypothetical extraterrestrial intelligence (ETI) signal originating from Barnard's star. These predictions are based on the star's physical properties and our observation strategy., Comment: 10 pages, 5 figures. matches the published version. arXiv admin note: text overlap with arXiv:2208.02421

For a system without spin-orbit coupling, the (i) nuclear plus electronic linear momentum and (ii) nuclear plus orbital electronic angular momentum are good quantum numbers. Thus, when a molecular system undergoes a nonadiabatic transition, there should be no change in the total linear or angular momentum. Now, the standard surface hopping algorithm ignores the electronic momentum and indirectly equates the momentum of the nuclear degrees of freedom to the total momentum. However, even with this simplification, the algorithm still does not conserve either the nuclear linear or the nuclear angular momenta. Here, we show that one way to address these failures is to dress the derivative couplings (i.e. the hopping directions) in two ways: (i) we disallow changes in the nuclear linear momentum by working in a translating basis (which is well known and leads to electron translation factors [ETFs]); and (ii) we disallow changes in the nuclear angular momentum by working in a basis that rotates around the center of mass (which is not well-known and leads to a novel, rotationally removable component of the derivative coupling that we will call electron rotation factors [ERFs] below, cf. Eq. 96). The present findings should be helpful in the short term as far as interpreting surface hopping calculations for singlet systems (without spin) and then developing new surface hopping algorithm in the long term for systems where one cannot ignore the electronic orbital and/or spin angular momentum.

Narrowband radio search for extraterrestrial intelligence (SETI) in the 21st century suffers severely from radio frequency interference (RFI), resulting in a high number of false positives, and it could be the major reason why we have not yet received any messages from space. We thereby propose a novel observation strategy, called MultiBeam Point-source Scanning (MBPS), to revolutionize the way RFI is identified in narrowband radio SETI and provide a prominent solution to the current situation. The MBPS strategy is a simple yet powerful method that sequentially scans over the target star with different beams of a telescope, hence creating real-time references in the time domain for cross-verification, thus potentially identifying all long-persistent RFI with a level of certainty never achieved in any previous attempts. By applying the MBPS strategy during the observation of TRAPPIST-1 with the FAST telescope, we successfully identified all 16,645 received signals as RFI using the solid criteria introduced by the MBPS strategy. Therefore we present the MBPS strategy as a promising tool that should bring us much closer to the first discovery of a genuine galactic greeting., Comment: 8 pages, 6 figures, published in The Astronomical Journal on Nov 15, 2023

We use resonant inelastic X-ray scattering (RIXS) at the Fe-L$_3$ edge to study the spin excitations of uniaxial-strained and unstrained FeSe$_{1-x}$S$_{x}$ ($0\leq x\leq0.21$) samples. The measurements on unstrained samples reveal dispersive spin excitations in all doping levels, which show only minor doping dependence in energy dispersion, lifetime, and intensity, indicating that high-energy spin excitations are only marginally affected by sulfur doping. RIXS measurements on uniaxial-strained samples reveal that the high-energy spin-excitation anisotropy observed previously in FeSe is also present in the doping range $0< x\leq0.21$ of FeSe$_{1-x}$S$_{x}$. The spin-excitation anisotropy persists to a high temperature up to $T>200$ K in $x=0.18$ and reaches a maximum around the nematic quantum critical doping ($x_c\approx0.17$). Since the spin-excitation anisotropy directly reflects the existence of nematic spin correlations, our results indicate that high-energy nematic spin correlations pervade the regime of nematicity in the phase diagram and are enhanced by the nematic quantum criticality. These results emphasize the essential role of spin fluctuations in driving electronic nematicity and open the door for uniaxial strain tuning of spin excitations in quantum materials hosting strong magnetoelastic coupling and electronic nematicity., Comment: 6 pages, 4 figures, supplemental materials uploaded

Privacy policies have become the most critical approach to safeguarding individuals' privacy and digital security. To enhance their presentation and readability, researchers propose the concept of contextual privacy policies (CPPs), aiming to fragment policies into shorter snippets and display them only in corresponding contexts. In this paper, we propose a novel multi-modal framework, namely SeePrivacy, designed to automatically generate contextual privacy policies for mobile apps. Our method synergistically combines mobile GUI understanding and privacy policy document analysis, yielding an impressive overall 83.6% coverage rate for privacy-related context detection and an accuracy of 0.92 in extracting corresponding policy segments. Remarkably, 96% of the retrieved policy segments can be correctly matched with their contexts. The user study shows SeePrivacy demonstrates excellent functionality and usability (4.5/5). Specifically, participants exhibit a greater willingness to read CPPs (4.1/5) compared to original privacy policies (2/5). Our solution effectively assists users in comprehending privacy notices, and this research establishes a solid foundation for further advancements and exploration.

The "search for extraterrestrial intelligence" (SETI) commensal surveys aim to scan the sky to find possible technosignatures from the extraterrestrial intelligence (ETI). The mitigation of radio frequency interference (RFI) is an important step, especially for the most sensitive Five-hundred-meter Aperture Spherical radio Telescope (FAST), which can detect more weak RFI. In this paper, we propose several new techniques for RFI mitigation, and use our procedure to search for ETI signals from the archival data of FAST's first SETI commensal survey. We detect the persistent narrowband RFI by setting a threshold of the signals' sky separation, and detect the drifting RFI (and potentially other types of RFI) using the Hough transform. We also use the clustering algorithms to remove more RFI and select candidates. The results of our procedure are compared to the earlier work on the same FAST data. We find that our methods, though relatively simpler in computation, remove more RFI (99.9912% compared to 99.9063% in the earlier work), but preserve the simulated ETI signals except those (5.1%) severely affected by the RFI. We also report more interesting candidate signals, about a dozen of which are new candidates that are not previously reported. In addition, we find that the proposed Hough transform method, with suitable parameters, also has the potential to remove the broadband RFI. We conclude that our methods can effectively remove the vast majority of the RFI while preserving and finding the candidate signals that we are interested in., Comment: 14 pages, 10 figures. AJ accepted

In this paper, we propose a novel method for distinguishing extraterrestrial intelligence (ETI) signals from radio frequency interference (RFI) by leveraging polarization features. We exploit the sinusoidal variation of the linearly polarized components of Stokes parameters with the parallactic angle as a characteristic signature of ETI signals, while such linearly polarized components remain relatively stable for terrestrial RFI. Typically, a minimum of 4-8 hours of observation time is required to detect these sinusoidal variations. The polarization approach in the search for extraterrestrial intelligence (SETI) also enables us to study the radio stellar bursts emitted by M-type stars as ancillary science, which is relevant to assessing the habitability of exoplanets. Compared to the frequency drift method, the polarization method effectively reduces the required observation time for signal identification while improving the signal identification process., Comment: 8 pages, 2 figures, published in The Astronomical Journal. Using polarization features as the criterion in SETI research

We prove both analytically and numerically that the total angular momentum of a molecular system undergoing adiabatic Born-Oppenheimer dynamics is conserved only when pseudo-magnetic Berry forces are taken into account. This finding sheds light on the nature of Berry forces for molecular systems with spin-orbit coupling and highlights how ab initio Born-Oppenheimer molecular dynamics simulations can successfully capture the entanglement of spin and nuclear degrees of freedom as modulated by electronic interactions.

The search for extraterrestrial intelligence (SETI) is to search for technosignatures associated with extraterrestrial life, such as engineered radio signals. In this paper, we apply the multibeam coincidence matching (MBCM) strategy, and propose a new search mode based on the MBCM which we call MBCM blind search mode. In our recent targeted SETI research, 33 exoplanet systems are observed by the Five-hundred-meter Aperture Spherical radio Telescope (FAST). With this blind search mode, we search for narrowband drifting signals across $1.05-1.45$ GHz in two orthogonal linear polarization directions separately. There are two special signals, one of which can only be detected by the blind search mode while the other can be found by both blind and targeted search modes. This result reveals huge advantages of the new blind search mode. However, we eliminate the possibility of the special signals being ETI signals based on much evidence, such as the polarization, drift, frequency and beam coverage characteristics. Our observations achieve an unprecedented sensitivity and our work provides a deeper understanding to the polarization analysis of extraterrestrial signals., Comment: 15 pages, 1 table, 7 figures. Matches AJ published version. Based on MBCM strategy by Zhen-Zhao Tao et al (2022 AJ 164 160), we propose a new search mode: MBCM blind search mode for FAST SETI observations

We investigate how the Berry force (i.e. the pseudo-magnetic force operating on nuclei as induced by electronic degeneracy and spin-orbit coupling (SOC)) might modify a post-transition state bifurcation (PTSB) reaction path and affect product selectivity for situations when multiple products share the same transition state. To estimate the magnitude of this effect, Langevin dynamics are performed on a model system with a valley-ridge inflection (VRI) point in the presence of a magnetic field (that mimics the Berry curvature). We also develop an analytic model for such selectivity that depends on key parameters such as the surface topology, the magnitude of the Berry force, and the nuclear friction. Within this dynamical model, static electronic structure calculations (at the level of generalized Hartree-Fock with spin-orbit coupling (GHF+SOC) theory) suggest that electronic-spin induced Berry force effects may indeed lead to noticeable changes in methoxy radical isomerization.

As a major approach to looking for life beyond the Earth, the search for extraterrestrial intelligence (SETI) is committed to detecting technosignatures such as engineered radio signals that are indicative of technologically capable life. In this paper, we report a targeted SETI campaign employing an observation strategy named multi-beam coincidence matching (MBCM) at the Five-hundred-meter Aperture Spherical radio Telescope (FAST) towards 33 known exoplanet systems, searching for ETI narrow-band drifting signals across 1.05-1.45 GHz in two orthogonal linear polarization directions separately. A signal at 1140.604 MHz detected from the observation towards Kepler-438 originally peaked our interest because its features are roughly consistent with assumed ETI technosignatures. However, evidences such as its polarization characteristics are almost able to eliminate the possibility of an extraterrestrial origin. Our observations achieve an unprecedented sensitivity since the minimum equivalent isotropic radiated power (EIRP) we are able to detect reaches 1.48 x10^9 W., Comment: 17 pages, 12 figures, matches the published version

The nuclear-electronic orbital (NEO) method is a well-established approach for treating nuclei quantum mechanically in molecular systems beyond the usual Born-Oppenheimer approximation. In this work, we present a strategy to implement the NEO method for periodic electronic structure calculations, particularly focused on multicomponent density functional theory (DFT). The NEO-DFT method is implemented in an all-electron electronic structure code, FHI-aims, using a combination of analytical and numerical integration techniques as well as a resolution of the identity scheme to enhance computational efficiency. After validating this implementation, proof-of-concept applications are presented to illustrate the effects of quantized protons on the physical properties of extended systems such as two-dimensional materials and liquid-semiconductor interfaces. Specifically, periodic NEO-DFT calculations are performed for a trans-polyacetylene chain, a hydrogen boride sheet, and a titanium oxide-water interface. The zero-point energy effects of the protons, as well as electron-proton correlation, are shown to noticeably impact the density of states and band structures for these systems. These developments provide a foundation for the application of multicomponent DFT to a wide range of other extended condensed matter systems., Comment: 8 figures

Molecular polaritons have become an emerging platform for remotely controlling molecular properties through strong light-matter interactions. Herein, a semiclassical approach is developed for describing molecular polaritons by self-consistently propagating the real-time dynamics of classical cavity modes and a quantum molecular subsystem described by the nuclear-electronic orbital (NEO) method, where electrons and specified nuclei are treated quantum mechanically on the same level. This semiclassical real-time NEO approach provides a unified description of electronic and vibrational strong couplings and describes the impact of the cavity on coupled nuclear-electronic dynamics while including nuclear quantum effects. For a single o-hydroxybenzaldehyde molecule under electronic strong coupling, this approach shows that the cavity suppression of excited state intramolecular proton transfer is influenced not only by the polaritonic potential energy surface but also by the timescale of the chemical reaction. This work provides the foundation for exploring collective strong coupling in nuclear-electronic quantum dynamical systems within optical cavities., Comment: manuscript (33 pages) + SI (13 pages) + TOC figure (1 page)

The origin of the electronic nematicity in FeSe is one of the most important unresolved puzzles in the study of iron-based superconductors. In both spin- and orbital-nematic models, the intrinsic magnetic excitations at $\mathbf{Q}_1=(1, 0)$ and $\mathbf{Q}_2=(0, 1)$ of twin-free FeSe are expected to provide decisive criteria for clarifying this issue. Although a spin-fluctuation anisotropy below 10 meV between $\mathbf{Q}_1$ and $\mathbf{Q}_2$ has been observed by inelastic neutron scattering around $T_c\sim 9$ K ($<

We studied the magnetic properties of YCu$_3$(OH)$_6$Br$_2$[Br$_{1-x}$(OH)$_{x}$] ($x$ = 0.33), where Cu$^{2+}$ ions form two-dimensional kagome layers. There is no magnetic order down to 50 mK while the Curie-Weiss temperature is on the order of -100 K. At zero magnetic field, the low-temperature specific heat shows a $T^2$ dependence. Above 2 T, a linear temperature dependence term in specific heat emerges, and the value of $\gamma = C/T$ increases linearly with the field. Furthermore, the magnetic susceptibility tends to a constant value at $T = 0$. Our results suggest that the magnetic ground state of YCu$_3$(OH)$_6$Br$_2$[Br$_{1-x}$(OH)$_{x}$] is consistent with a Dirac quantum-spin-liquid state with a linearly dispersing spinon strongly coupled to an emergent gauge field, which has long been theoretically proposed as a candidate ground state in the two-dimensional kagome Heisenberg antiferromagnetic system., Comment: 7 pages, 3 figures

The computational investigation of photochemical processes often entails the calculation of excited state geometries, energies, and energy gradients. The nuclear-electronic orbital (NEO) approach treats specified nuclei, typically protons, quantum mechanically on the same level as the electrons, thereby including the associated nuclear quantum effects and non-Born-Oppenheimer behavior into quantum chemistry calculations. The multicomponent density functional theory (NEO-DFT) and time-dependent DFT (NEO-TDDFT) methods allow efficient calculations of ground and excited states, respectively. Herein, the analytical gradients are derived and implemented for the NEO-TDDFT method and the associated Tamm-Dancoff approximation (NEO-TDA). The programmable equations for these analytical gradients, as well as the NEO-DFT analytical Hessian, are provided. The NEO approach includes the anharmonic zero-point energy and density delocalization associated with the quantum protons, as well as vibronic mixing, in geometry optimizations and energy calculations of ground and excited states. The harmonic zero-point energy associated with the other nuclei can be computed via the NEO Hessian. This approach is used to compute the 0-0 adiabatic excitation energies for a set of nine small molecules with all protons quantized, exhibiting slight improvement over the conventional electronic approach. Geometry optimizations of two excited state intramolecular proton transfer systems are performed with one and two quantized protons, respectively. The NEO calculations for these systems produce electronically excited state geometries with stronger intramolecular hydrogen bonds and similar relative stabilities compared to conventional electronic methods. This work provides the foundation for nonadiabatic dynamics simulations of fundamental processes such as photoinduced proton transfer and proton-coupled electron transfer.

Triangular lattice of rare-earth ions with interacting effective spin-$1/2$ local moments is an ideal platform to explore the physics of quantum spin liquids (QSLs) in the presence of strong spin-orbit coupling, crystal electric fields, and geometrical frustration. The Yb delafossites, NaYbCh$_2$ (Ch=O, S, Se) with Yb ions forming a perfect triangular lattice, have been suggested to be candidates for QSLs. Previous thermodynamics, nuclear magnetic resonance, and muon spin rotation measurements on NaYbCh$_2$ have supported the suggestion of the QSL ground states. The key signature of a QSL, the spin excitation continuum, arising from the spin quantum number fractionalization, has not been observed. Here we perform both elastic and inelastic neutron scattering measurements as well as detailed thermodynamic measurements on high-quality single-crystalline NaYbSe$_2$ samples to confirm the absence of long-range magnetic order down to 40 mK, and further reveal a clear signature of magnetic excitation continuum extending from 0.1 to 2.5 meV. The comparison between the structure of the magnetic excitation spectra and the theoretical expectation from the spinon continuum suggests that the ground state of NaYbSe$_2$ is a QSL with a spinon Fermi surface., Comment: 18 pages, 6 figures