arXiv subjects

Nicholas Clark

Publications and source records attributed to Nicholas Clark.

At least 19 recordsLinked to original sources

arXiv2026

Momentum-space engineering in van der Waals heterostructures

Twenty years of graphene research have established Dirac fermions as a versatile platform for exploring quantum topological phenomena. Yet control over graphene's low-energy spectrum mostly follows the route of miniband engineering using real-space superlattices. Here we introduce a complementary approach based on momentum-space 'Umklapp' band engineering. This is realised by matching reciprocal space positions of band edges of two adjacent highly incommensurate 2D crystals to coincide upon a boost from their Bragg vectors, creating resonant interlayer hybridisation that qualitatively reconstructs their spectra. To demonstrate this approach experimentally, we use monolayer graphene on MoS$_2$, twisted such that MoS$_2$ Q-valley states are brought by Umklapp into energy-momentum resonance with graphene's Dirac cones. The ensuing hybridization results in the formation of a clear additional Dirac-like spectral feature, identified by a distinct Landau-level fan and Shubnikov-de Haas oscillations characteristic to Berry phase $π$ electrons. These new topological spectral features create a spin-valley locked Ising system which is robust against small twist-angle variations that can be further tuned by an external displacement field. More broadly, Umklapp band engineering offers a practical strategy for tailoring the electronic structure in van der Waals heterostructures, expanding the design space of quantum materials beyond moiré superlattices and weak proximity effects.

cond-mat.mes-hall↗

arXiv2026

JWST observations of the planetary nebula NGC 6302 IV: PAH spectral characteristics, formation and evolution

Polycyclic aromatic hydrocarbons (PAHs) and carbonaceous dust have been observed in Oxygen-rich planetary nebulae (PNe), yet their formation and evolution in these environments is an open question. We aim to study the formation and evolution of the PAHs in the O-rich PN NGC 6302, by characterizing the PAH emission throughout this object. We obtained JWST MIRI IFU spectroscopic observations of NGC 6302 pointed at its central source. From these, we extract four template spectra that are representative of the variation in PAH emission throughout NGC 6302. We detect the major PAH features at 6.2, 7.7, 8.6, 11.2, and 12.7 $μ$m, and several minor PAH features. The template spectra vary in terms of their PAH feature widths, peak wavelengths, and relative intensities. The 11.2 $μ$m PAH feature is class B, typical for PNe. The 6-9 $μ$m PAH features are class A, which is less common for PNe. We estimate the PAH charge to be 75% cations on average, based on the 7.7/11.2 PAH feature ratio. The relative strengths of the 11-15 $μ$m PAH features indicate a range of PAH edge structures. To ensure consistency in our observations and explain variable PAH feature widths, we propose a variation in the size of the PAHs throughout NGC 6302, and suggest variation in the shielding of these PAHs. The PAHs range from large and non-compact, to small and compact. We find that NGC 6302 formed PAHs in-situ in the current PN phase, likely from small hydrocarbons formed by the photodissociation of CO.

astro-ph.GA↗

arXiv2026

The JWST Proto-PAH Project: Detection of the methyl radical CH$_{3}$ in the highly evolved C-rich object SMP LMC 011

We report the first detection of the neutral methyl radical CH$_3$ in a highly evolved C-rich object, SMP LMC 011, using JWST MIRI/MRS. CH$_3$ is well fitted by an excitation temperature of $T_{\rm ex} \simeq$~190\,K and a column density of $N_{\rm tot}(\mathrm{CH_3}) \simeq 5.6\times10^{17}$ cm$^{-2}$. We also report the non-detection of ethane (C$_2$H$_6$), consistent with CH$_3$ reacting preferentially with unsaturated radicals rather than self-recombination, which may be inefficient in SMP LMC 011. Combined with the exceptionally large benzene column density of SMP LMC 011, this supports a methyl-addition route from benzene towards alkyl-substituted aromatics. We propose that the high CH$_3$ abundance is driven by the erosion of hydrogenated amorphous carbon (HAC) dust grains in the dense warm torus by UV photons from the central star and/or by shocks, which release CH$_3$ directly into the gas phase. These results establish CH$_3$ as a key reactive intermediate in the formation of complex hydrocarbons in C-rich circumstellar environments. Chemical models that incorporate methyl-addition reactions are needed for a better understanding of PAH formation pathways in evolved stars. The potential detection of alkyl-substituted aromatics such as toluene (C$_7$H$_8$) and ethylbenzene (C$_8$H$_{10}$) in C-rich evolved stars would provide direct confirmation of CH$_3$-driven aromatic growth in circumstellar environments.

astro-ph.SR↗

arXiv2026

Moiré-induced lattice reconstruction at buried atomic interfaces

Atomic reconstruction at twisted two-dimensional interfaces governs many of their emergent optical, electronic, and mechanical properties, including sliding ferroelectricity. Despite recent progress in understanding lattice reconstruction in suspended twisted bilayers, structural changes at van der Waals heterointerfaces between multilayer crystals remain largely unexplored. Here we use multi-slice electron ptychography to non-invasively recover the three-dimensional atomic structure at marginally twisted rhombohedral interfaces between thick transition-metal dichalcogenide crystals. With a position precision of ~3 pm and a depth resolution ~1 nm, we resolve the twist-induced lattice reconstruction field per layer, and the resulting dislocation network at the buried interface. Despite the bulk nature, we observe markedly strong in-plane interfacial reconstruction due to suppression of the out-of-plane bending by outer layers, exceeding predictions from our three-dimensional modelling. Furthermore, we extract the strain tensor evolution during the decay of the reconstruction into the bulk, providing a structural foundation for understanding multi-layer moiré systems.

cond-mat.mes-hall↗

arXiv2026

Spontaneous Persuasion: An Audit of Model Persuasiveness in Everyday Conversations

Large language models (LLMs) possess strong persuasive capabilities that outperform humans in head-to-head comparisons. Users report consulting LLMs to inform major life decisions in relationships, medical settings, and when seeking professional advice. Prior work measures persuasion as intentional attempts at producing the most effective argument or convincing statement. This fails to capture everyday human-AI interactions in which users seek information or advice. To address this gap, we introduce "spontaneous persuasion," which characterizes the inexplicit use of persuasive strategies in everyday scenarios where persuasion is not necessarily warranted. We conduct an audit of five LLMs to uncover how frequently and through which techniques spontaneous persuasion appears in multi-turn conversations. To simulate response styles, we provide a user response taxonomy grounded in literature from psychology, communication, and linguistics. Furthermore, we compare the distribution of spontaneous persuasion produced by LLMs with human responses on the same topics, collected from Reddit. We find LLMs spontaneously persuade the user in virtually all conversations, heavily relying on information-based strategies such as appeals to logic or quantitative evidence. This was consistent across models and user response styles, but conversations concerning mental health saw higher rates of appraisal-based and emotion-based strategies. In comparison, human responses tended to invoke strategies that generate social influence, like negative emotion appeals and non-expert testimony. This difference may explain the effectiveness of LLM in persuading users, as well as the perception of models as objective and impartial.

cs.HC↗

arXiv2026

Detection of CO$_2$ ice in the planetary nebula NGC 6302

Using JWST/MIRI observations, we report the detection of CO$_2$ ice in the dusty torus of the planetary nebula NGC 6302, an environment generally considered hostile to fragile molecular species and ices due to intense UV irradiation. This detection accompanies cold (20-50 K) gas-phase CO$_2$ along the same sightlines. The ice absorption profile exhibits a double-peak profile, a characteristic of pure, crystalline CO$_2$ ice. The CO$_2$ gas-to-ice ratio is more than an order of magnitude higher than in young stellar objects, pointing to distinct ice formation or processing mechanisms in evolved stellar environments. This discovery demonstrates that the dusty torus provides sufficient shielding to harbour ice chemistry, and that ice-mediated surface reactions must be incorporated into chemical models of planetary nebulae.

astro-ph.GA↗

arXiv2025

Offscript: Automated Auditing of Instruction Adherence in LLMs

Large Language Models (LLMs) and generative search systems are increasingly used for information seeking by diverse populations with varying preferences for knowledge sourcing and presentation. While users can customize LLM behavior through custom instructions and behavioral prompts, no mechanism exists to evaluate whether these instructions are being followed effectively. We present Offscript, an automated auditing tool that efficiently identifies potential instruction following failures in LLMs. In a pilot study analyzing custom instructions sourced from Reddit, Offscript detected potential deviations from instructed behavior in 86.4% of conversations, 22.2% of which were confirmed as material violations through human review. Our findings suggest that automated auditing serves as a viable approach for evaluating compliance to behavioral instructions related to information seeking.

cs.HC↗

arXiv2025

ValueCompass: A Framework for Measuring Contextual Value Alignment Between Human and LLMs

As AI systems become more advanced, ensuring their alignment with a diverse range of individuals and societal values becomes increasingly critical. But how can we capture fundamental human values and assess the degree to which AI systems align with them? We introduce ValueCompass, a framework of fundamental values, grounded in psychological theory and a systematic review, to identify and evaluate human-AI alignment. We apply ValueCompass to measure the value alignment of humans and large language models (LLMs) across four real-world scenarios: collaborative writing, education, public sectors, and healthcare. Our findings reveal concerning misalignments between humans and LLMs, such as humans frequently endorse values like "National Security" which were largely rejected by LLMs. We also observe that values differ across scenarios, highlighting the need for context-aware AI alignment strategies. This work provides valuable insights into the design space of human-AI alignment, laying the foundations for developing AI systems that responsibly reflect societal values and ethics.

cs.HC↗

arXiv2025

Mind the Value-Action Gap: Do LLMs Act in Alignment with Their Values?

Existing research primarily evaluates the values of LLMs by examining their stated inclinations towards specific values. However, the "Value-Action Gap," a phenomenon rooted in environmental and social psychology, reveals discrepancies between individuals' stated values and their actions in real-world contexts. To what extent do LLMs exhibit a similar gap between their stated values and their actions informed by those values? This study introduces ValueActionLens, an evaluation framework to assess the alignment between LLMs' stated values and their value-informed actions. The framework encompasses the generation of a dataset comprising 14.8k value-informed actions across twelve cultures and eleven social topics, and two tasks to evaluate how well LLMs' stated value inclinations and value-informed actions align across three different alignment measures. Extensive experiments reveal that the alignment between LLMs' stated values and actions is sub-optimal, varying significantly across scenarios and models. Analysis of misaligned results identifies potential harms from certain value-action gaps. To predict the value-action gaps, we also uncover that leveraging reasoned explanations improves performance. These findings underscore the risks of relying solely on the LLMs' stated values to predict their behaviors and emphasize the importance of context-aware evaluations of LLM values and value-action gaps.

cs.HC↗

arXiv2025

Detection of CH3+ in the O-rich planetary nebula NGC 6302

Planetary nebulae are sites where ejected stellar material evolves into complex molecules, but the precise physical conditions and chemical routes that govern these processes are unclear. The presence of abundant carbon-rich molecules in O-rich environments poses particular challenges. Here we report the first detection of methyl cation (CH3+) in any planetary nebula, observed in the O-rich nebula NGC 6302 using JWST MIRI/MRS observations. CH3+ is a key driver of organic chemistry in UV-irradiated environments. Spatially resolved observations reveal that CH3+ is co-located with 12CO, H2, H II, HCO+, and Polycyclic aromatic hydrocarbons (PAHs). LTE modelling of the CH3+ emission yields excitation temperatures of 500-800K in the inner bubble and torus, rising to 1000-2000K in the outer bubble of NGC 6302, with column densities ranging from ~10^11 to 10^13 cm^-2. This detection demonstrates that hydrocarbon radical chemistry must be incorporated into planetary nebulae chemical models. Further near-IR observations are crucial to map different chemical networks operating in these environments.

astro-ph.GA↗

arXiv2025

The JWST/MIRI view of the planetary nebula NGC 6302 I.: a UV irradiated torus and a hot bubble triggering PAH formation

NGC 6302 is a spectacular bipolar planetary nebula (PN) whose spectrum exhibits fast outflows and highly ionized emission lines, indicating the presence of a very hot central star (~220,000 K). Its infrared spectrum reveals a mixed oxygen and carbon dust chemistry, displaying both silicate and polycyclic aromatic hydrocarbon (PAH) features. Using the JWST Mid-Infrared Instrument (MIRI) and Medium Resolution Spectrometer, a mosaic map was obtained over the core of NGC 6302, covering the wavelength range of 5--28 micron and spanning an area of ~18.5 arcsec x15 arcsec. The spatially resolved spectrum reveals ~200 molecular and ionized lines from species requiring ionisation potentials of up to 205 eV. The spatial distributions highlight a complex structure at the nebula's centre. Highly ionized species such as Mg VII and Si VII show compact structures, while lower-ionization species such as H^+ extend much farther outwards, forming filament-defined rims that delineate a bubble. Within the bubble, the H^+ and H_2 emission coincide, while the PAH emission appears farther out, indicating an ionization structure distinct from typical photodissociation regions, such as the Orion Bar. This may be the first identification of a PAH formation site in a PN. This PN appears to be shaped not by a steady, continuous outflow, but by a series of dynamic, impulsive bubble ejections, creating local conditions conducive to PAH formation. A dusty torus surrounds the core, primarily composed of large (micron-sized) silicate grains with crystalline components. The long-lived torus contains a substantial mass of material, which could support an equilibrium chemistry and a slow dust-formation process.

astro-ph.SR↗

arXiv2025

JWST observations of the Ring Nebula (NGC 6720) -- II. PAH emission

Polycyclic aromatic hydrocarbons (PAHs) and carbonaceous dust have been observed in clumpy circumstellar environments, yet their formation and evolutionary pathways in such environments remain elusive. We aim to characterize the PAH emission in a clumpy planetary nebula to decipher their formation and evolution pathways. We obtained JWST Near-Infrared Spectrograph (NIRSpec) and Mid-Infrared Instrument (MIRI) integral field unit spectroscopic observations of two individual knots in the Ring Nebula (NGC 6720), a clumpy planetary nebula, and determine the PAH spectral characteristics. We detect the 3.3 and 11.2 um PAH emission bands in both knots but do not detect PAH emission in the 6-9 um range. We supplement our data with Spitzer Infrared Spectrograph (IRS) Short-Low 1 (SL1) and SL2 data, containing 11.2, weak 6.2, and weak 7.7 um PAH emission bands. The JWST data confirm the unusual profile of the 11.2 um band, which is very broad and redshifted with respect to typical 11.2 um PAH profiles. We estimate the PAH population to be largely neutral. The relative integrated surface brightness of the 3.3 and 11.2 um bands indicates the presence of small-sized PAHs, consisting of 35 +/- 6 carbon atoms. We find that the PAH emission is concentrated outside of the clumps, in the inter-clump medium, and confirm the existence of enhanced PAH emission in a narrow 'PAH ring' centred on the central star. This morphology suggests that PAHs formed during the Ring Nebula's asymptotic giant branch phase, in the central star's dust-driven wind.

astro-ph.SR↗

arXiv2025

The 2D Materials Roadmap

Over the past two decades, 2D materials have rapidly evolved into a diverse and expanding family of material platforms. Many members of this materials class have demonstrated their potential to deliver transformative impact on fundamental research and technological applications across different fields. In this roadmap, we provide an overview of the key aspects of 2D material research and development, spanning synthesis, properties and commercial applications. We specifically present roadmaps for high impact 2D materials, including graphene and its derivatives, transition metal dichalcogenides, MXenes as well as their heterostructures and moiré systems. The discussions are organized into thematic sections covering emerging research areas (e.g., twisted electronics, moiré nano-optoelectronics, polaritronics, quantum photonics, and neuromorphic computing), breakthrough applications in key technologies (e.g., 2D transistors, energy storage, electrocatalysis, filtration and separation, thermal management, flexible electronics, sensing, electromagnetic interference shielding, and composites) and other important topics (computational discovery of novel materials, commercialization and standardization). This roadmap focuses on the current research landscape, future challenges and scientific and technological advances required to address, with the intent to provide useful references for promoting the development of 2D materials.

cond-mat.mtrl-sci↗

arXiv2025

JWST observations of the Ring Nebula (NGC 6720): III. A dusty disk around its Central Star

The planetary nebula NGC 6720, also known as the ``Ring Nebula", is one of the most iconic examples of nearby planetary nebulae whose morphologies present a challenge to our theoretical understanding of the processes that govern the deaths of most stars in the Universe that evolve on a Hubble time. We present new imaging with JWST of the central star of this planetary nebula (CSPN) and its close vicinity, in the near- to mid-IR wavelength range. We find the presence of a dust cloud around the CSPN, both from the spectral energy distribution at wavelengths >~5 micron, as well as radially-extended emission in the 7.7, 10 and 11.3 micron images. From modeling of these data, we infer that the CSPN has a luminosity of 310 Lsun and is surrounded by a dust cloud with a size of ~2600 au, consisting of relatively small amorphous silicate dust grains (radius ~0.01 micron) with a total mass of 1.9 x 10^(-6) M_earth. However, our best-fit model shows a significant lack of extended emission at 7.7 micron -- we show that such emission can arise from a smaller (7.3 x 10^(-7) M_earth) but uncertain mass of (stochastically-heated) ionized PAHs. However, the same energetic radiation also rapidly destroys PAH molecules, suggesting that these are most likely being continuously replenished, via the outgassing of cometary bodies and/or the collisional grinding of planetesimals. We also find significant photometric variability of the central source that could be due to the presence of a close dwarf companion of mass < ~0.1 Msun.

astro-ph.SR↗

arXiv2025

Epistemic Alignment: A Mediating Framework for User-LLM Knowledge Delivery

LLMs increasingly serve as tools for knowledge acquisition, yet users cannot effectively specify how they want information presented. When users request that LLMs "cite reputable sources," "express appropriate uncertainty," or "include multiple perspectives," they discover that current interfaces provide no structured way to articulate these preferences. The result is prompt sharing folklore: community-specific copied prompts passed through trust relationships rather than based on measured efficacy. We propose the Epistemic Alignment Framework, a set of ten challenges in knowledge transmission derived from the philosophical literature of epistemology, concerning issues such as evidence quality assessment and calibration of testimonial reliance. The framework serves as a structured intermediary between user needs and system capabilities, creating a common vocabulary to bridge the gap between what users want and what systems deliver. Through a thematic analysis of custom prompts and personalization strategies shared on online communities where these issues are actively discussed, we find users develop elaborate workarounds to address each of the challenges. We then apply our framework to two prominent model providers, OpenAI and Anthropic, through content analysis of their documented policies and product features. Our analysis shows that while these providers have partially addressed the challenges we identified, they fail to establish adequate mechanisms for specifying epistemic preferences, lack transparency about how preferences are implemented, and offer no verification tools to confirm whether preferences were followed. For AI developers, the Epistemic Alignment Framework offers concrete guidance for supporting diverse approaches to knowledge; for users, it works toward information delivery that aligns with their specific needs rather than defaulting to one-size-fits-all approaches.

cs.HC↗

arXiv2024

LLM Confidence Evaluation Measures in Zero-Shot CSS Classification

Assessing classification confidence is critical for leveraging large language models (LLMs) in automated labeling tasks, especially in the sensitive domains presented by Computational Social Science (CSS) tasks. In this paper, we make three key contributions: (1) we propose an uncertainty quantification (UQ) performance measure tailored for data annotation tasks, (2) we compare, for the first time, five different UQ strategies across three distinct LLMs and CSS data annotation tasks, (3) we introduce a novel UQ aggregation strategy that effectively identifies low-confidence LLM annotations and disproportionately uncovers data incorrectly labeled by the LLMs. Our results demonstrate that our proposed UQ aggregation strategy improves upon existing methods andcan be used to significantly improve human-in-the-loop data annotation processes.

cs.HC↗

arXiv2024

Tunnel junctions based on interfacial 2D ferroelectrics

Van der Waals (vdW) heterostructures have opened new opportunities to develop atomically thin (opto)electronic devices with a wide range of functionalities. The recent focus on manipulating the interlayer twist angle has led to the observation of out-of-plane room temperature ferroelectricity in twisted rhombohedral (R) bilayers of transition metal dichalcogenides (TMDs). Here we explore the switching behaviour of sliding ferroelectricity using scanning probe microscopy domain mapping and tunnelling transport measurements. We observe well-pronounced ambipolar switching behaviour in ferroelectric tunnelling junctions (FTJ) with composite ferroelectric/non-polar insulator barriers and support our experimental results with complementary theoretical modelling. Furthermore, we show that the switching behaviour is strongly influenced by the underlying domain structure, allowing fabrication of diverse FTJ devices with various functionalities. We show that to observe the polarisation reversal, at least one partial dislocation must be present in the device area. This behaviour is drastically different from that of conventional ferroelectric materials and its understanding is an important milestone for future development of optoelectronic devices based on sliding ferroelectricity.

cond-mat.mes-hall↗

arXiv2024

LLMs Among Us: Generative AI Participating in Digital Discourse

The emergence of Large Language Models (LLMs) has great potential to reshape the landscape of many social media platforms. While this can bring promising opportunities, it also raises many threats, such as biases and privacy concerns, and may contribute to the spread of propaganda by malicious actors. We developed the "LLMs Among Us" experimental framework on top of the Mastodon social media platform for bot and human participants to communicate without knowing the ratio or nature of bot and human participants. We built 10 personas with three different LLMs, GPT-4, LLama 2 Chat, and Claude. We conducted three rounds of the experiment and surveyed participants after each round to measure the ability of LLMs to pose as human participants without human detection. We found that participants correctly identified the nature of other users in the experiment only 42% of the time despite knowing the presence of both bots and humans. We also found that the choice of persona had substantially more impact on human perception than the choice of mainstream LLMs.

cs.HC↗