arXiv subjects

Chen Qu

Publications and source records attributed to Chen Qu.

At least 19 recordsLinked to original sources

arXiv2026

VPT2 Calculations of Vibrational Energies of CH3COOC6H4COOH Done in Seconds on a Laptop Using a Machine Learned Potential

The determination of quartic force fields for use in vibrational second-order perturbation (VPT2) calculations, currently available in numerous electronic structure packages, becomes very expensive as the size of the molecule increases, especially if high-level coupled cluster theory is used. Machine-learned potentials (MLPs) for large molecules and clusters offer a viable alternative to obtain the quartic force field (QFF). Here, we report Fortran and Python software to determine the QFF and perform VPT2 calculations of energies from MLPs. We describe this software briefly and then apply it to \ce{H2O} and protonated oxalate as test cases. The Fortran software is applied to 21-atom aspirin, using a fast MLP reported by us. Despite the fact that there are 32,509 unique cubic force constants for aspirin, the computer time to calculate them using this MLP is trivial, i.e., around one minute. These results are the first quantum anharmonic ones for such a large molecule. The present protocol offers an efficient way to study quantum anharmonic effects for vibrational energies in large molecules. Currently, these are obtained overwhelmingly from classical molecular dynamics simulations, which cannot describe strong anharmonicity.

physics.chem-ph↗

arXiv2026

Fidelity of Machine Learned Potentials: Quantitative Assessment for Protonated Oxalate

There has been a veritable explosion of methods and software to perform machine-learned regression on datasets of electronic energies and forces to develop high-dimensional machine learned potential energy surfaces (ML-PESs). A major, but not deeply-studied aspect is how well different ML-PESs represent the same dataset on which they are trained, beyond the standard fitting precision metrics. Here, this is examined in detail using several ''stress tests'', for two widely applied machine-learned potential approaches. One is based on permutationally invariant polynomial (PIP) linear least square regression and the other is the message-passing neural network PhysNet approach. These potentials and dipole moment surfaces are used in VSCF/VCI calculations of vibrational energies and wavefunctions. The energies from the two PESs are directly compared as are the IR spectra. In addition, tunneling splittings for the hydrogen transfer between two equivalent structures are reported from using three methods: ring polymer instanton theory, diffusion Monte Carlo simulations, and the $Q_{im}$ path method. These calculations require the evaluation of on the order of one billion energies that are widely dispersed in the 15-dimensional configurational space. The two PESs yield results for these quantities in excellent agreement with each other.

physics.chem-ph↗

arXiv2026

EgoReasoner: Learning Egocentric 4D Reasoning via Task-Adaptive Structured Thinking

Egocentric video understanding is inherently complex due to the dynamic 4D nature of the environment, where camera motion and object displacements necessitate a continuous re-evaluation of spatial relations. In this work, we target a suite of under-explored egocentric 4D reasoning tasks, including fixture interaction counting, viewpoint-relative fixture location, object movement itinerary tracking, and stationary object localization, that require fundamentally different cognitive operations: spatial anchoring, temporal tracking, and duration reasoning. We observe that these structural differences make task-agnostic approaches insufficient: generic Chain-of-Thought methods lack task-appropriate reasoning primitives, and uniform reinforcement learning actively destabilizes performance on spatial tasks. To address this, we propose EgoReasoner, a two-stage framework that aligns both the reasoning scaffold and the reward signal to each task's cognitive structure. In the first stage, Task-Adaptive Thinking Templates guide the synthesis of structured CoT traces that teach the model to reason adaptively across task types via supervised fine-tuning. In the second stage, task-aware reward functions verify entity grounding, temporal alignment, and task-adaptive logical consistency, selectively strengthening each reasoning pathway via reinforcement fine-tuning with GRPO. Our 3B-parameter model, trained on only 16K samples, achieves 37.5% average accuracy on the challenging HD-EPIC benchmark, surpassing Qwen2.5-VL-7B (25.7%) by over 10 points.

cs.CV↗

arXiv2026

Monomeric machine learning potential for general covalent molecules: linear alkanes as an example

Machine-learning potentials (MLPs) have become important tools for modern molecular simulations. However, developing models that simultaneously achieve high accuracy and high computational efficiency remains a significant challenge. In this work, we extend the recently proposed MB-PIPNet framework to general covalently bonded molecular systems by combining monomer-based energy decomposition, permutationally invariant polynomial (PIP) descriptors, and neural networks within a fragmentation-based strategy. Within this framework, the total potential energy is represented as a sum of effective monomeric contributions, where PIPs provide compact and chemically motivated descriptions of both monomer internal structures and their local chemical environments. As a proof-of-concept application, we apply the MB-PIPNet framework to linear alkanes, using n-Tetradecane as a representative system, and benchmark its performance against established atomistic machine-learning models. The resulting MB-PIPNet potential accurately reproduces reference ab initio electronic energies and reliably captures key molecular properties, including torsional potential energy profiles, harmonic vibrational frequencies, and vibrational power spectra obtained from molecular dynamics simulations. Importantly, MB-PIPNet demonstrates a substantial advantage in computational efficiency over other MLP models for combined energy and force evaluations. These results establish MB-PIPNet as a scalable and efficient framework for constructing MLPs, providing an additional route for large-scale quantum and classical simulations of complex molecular systems.

physics.chem-ph↗

arXiv2026

Reinforced Attention Learning

Post-training with Reinforcement Learning (RL) has substantially improved reasoning in Large Language Models (LLMs) via test-time scaling. However, extending this paradigm to Multimodal LLMs (MLLMs) through verbose rationales yields limited gains for perception and can even degrade performance. We propose Reinforced Attention Learning (RAL), a policy-gradient framework that directly optimizes internal attention distributions rather than output token sequences. By shifting optimization from what to generate to where to attend, RAL promotes effective information allocation and improved grounding in complex multimodal inputs. Experiments across diverse image and video benchmarks show consistent gains over GRPO and other baselines. We further introduce On-Policy Attention Distillation, demonstrating that transferring latent attention behaviors yields stronger cross-modal alignment than standard knowledge distillation. Our results position attention policies as a principled and general alternative for multimodal post-training.

cs.CL↗

arXiv2025

"Gold-Standard" $\Delta$-Machine Learned and Transferable Potential for Linear Alkanes

The conformational properties of linear alkanes, C$_n$H$_{2n+2}$, have been of intense interest for many years. Experiments and corresponding electronic structure calculations were first reported in the mid-2000s and continue to the present time. These focus on the minimum chain length where the transition from the linear minimum to the hairpin minimum occurs. We recently reported a transferable many-body permutationally invariant polynomial (MB-PIP) for linear alkanes using B3LYP electronic energies, which do not account for dispersion. Here we report a $\Delta$-ML approach to elevate this B3LYP-based and new PBE0+MBD MB-PIP potentials using PNO-LCCSD(T)-F12 energies. The new $\Delta$-corrected potentials predict the difference in these minima accurately, compared to benchmark CCSD(T) results, over the range C$_{12}$H$_{28}$ to C$_{28}$H$_{58}$. Vibrational power spectra are also reported for C$_{14}$H$_{30}$ and C$_{30}$H$_{62}$ using the uncorrected and $\Delta$-ML B3LYP. These new PIP-MB potentials for linear alkanes are the most accurate ones currently available and can be used in studies of properties of linear alkanes.

physics.chem-ph↗

arXiv2025

The quantum nature of ubiquitous vibrational features revealed for ethylene glycol

Vibrational properties of molecules are of widespread interest and importance in chemistry and biochemistry. The reliability of widely employed approximate computational methods is questioned here against the complex experimental spectrum of ethylene glycol. Comparisons between quantum vibrational self-consistent field and virtual-state configuration interaction (VSCF/VCI), adiabatically switched semiclassical initial value representation (AS SCIVR), and thermostatted ring polymer molecular dynamics (TRPMD) calculations are made using a full-dimensional machine-learned potential energy surface. Calculations are done for five low-lying conformers and compared with the experiment, with a focus on the high-frequency, OH-stretches, and CH-stretches, part of the spectrum. Fermi resonances are found in the analysis of VSCF/VCI eigenstates belonging to the CH-stretching band. Results of comparable accuracy, quality, and level of detail are obtained by means of AS SCIVR. The current VSCF/VCI and AS-SCIVR power spectra largely close the gaps between the experiment and TRPMD and classical MD calculations. Analysis of these results provide guidance on what level of accuracy to expect from TRPMD and classical MD calculations of the vibrational spectra for ubiquitous CH and OH-stretches bands. This work shows that even general vibrational features require a proper quantum treatment usually not achievable by the most popular theoretical approaches.

physics.chem-ph↗

arXiv2024

Extending the atomic decomposition and many-body representation, a chemistry-motivated monomer-centered approach for machine learning potentials

Most widely used machine learned (ML) potentials for condensed phase applications rely on many-body permutationally invariant polynomial (PIP) or atom-centered neural networks (NN). However, these approaches often lack chemical interpretability in atomistic energy decomposition and the computational efficiency of traditional force fields has not been fully achieved. Here, we present a novel method that combines aspects of both approaches, and achieves state-of-the-art balance of accuracy and force field-level speed. This method utilizes a monomer-centered representation, where the potential energy is decomposed into the sum of chemically meaningful monomeric energies. Without sophisticated neural network design, the structural descriptors of monomers are described by 1-body and 2-body effective interactions, enforced by appropriate sets of PIPs as inputs to the feed forward NN. We demonstrate the performance of this method through systematic assessments of models for gas-phase water trimer, liquid water, and also liquid CO2. The high accuracy, fast speed, and flexibility of this method provide a new route for constructing accurate ML potentials and enabling large-scale quantum and classical simulations for complex molecular systems.

physics.chem-ph↗

arXiv2024

Inelastic Triatom-Atom Quantum Close-Coupling Dynamics in Full Dimensionality: all rovibrational mode quenching of water due to H impact on a six-dimensional potential energy surface

The rovibrational level populations, and subsequent emission in various astrophysical environments, is driven by inelastic collision processes. The available rovibrational rate coefficients for water have been calculated using a number of approximations. We present a numerically exact calculation for the rovibrational quenching for all water vibrational modes due to collisions with atomic hydrogen. The scattering theory implements a quantum close-coupling (CC) method on a high level ab initio six-dimensional (6D) potential energy surface (PES). Total rovibrational quenching cross sections for excited bending levels were compared with earlier results on a 4D PES with the rigid-bender close-coupling (RBCC) approximation. General agreement between 6D-CC and 4D-RBCC calculations are found, but differences are evident including the energy and amplitude of low-energy orbiting resonances. Quenching cross sections from the symmetric and asymmetric stretch modes are provided for the first time. The current 6D-CC calculation provides accurate inelastic data needed for astrophysical modeling.

astro-ph.GA↗

arXiv2024

FedMCP: Parameter-Efficient Federated Learning with Model-Contrastive Personalization

With increasing concerns and regulations on data privacy, fine-tuning pretrained language models (PLMs) in federated learning (FL) has become a common paradigm for NLP tasks. Despite being extensively studied, the existing methods for this problem still face two primary challenges. First, the huge number of parameters in large-scale PLMs leads to excessive communication and computational overhead. Second, the heterogeneity of data and tasks across clients poses a significant obstacle to achieving the desired fine-tuning performance. To address the above problems, we propose FedMCP, a novel parameter-efficient fine-tuning method with model-contrastive personalization for FL. Specifically, FedMCP adds two lightweight adapter modules, i.e., the global adapter and the private adapter, to the frozen PLMs within clients. In a communication round, each client sends only the global adapter to the server for federated aggregation. Furthermore, FedMCP introduces a model-contrastive regularization term between the two adapters. This, on the one hand, encourages the global adapter to assimilate universal knowledge and, on the other hand, the private adapter to capture client-specific knowledge. By leveraging both adapters, FedMCP can effectively provide fine-tuned personalized models tailored to individual clients. Extensive experiments on highly heterogeneous cross-task, cross-silo datasets show that FedMCP achieves substantial performance improvements over state-of-the-art FL fine-tuning approaches for PLMs.

cs.CL↗

arXiv2024

Can We Learn the Energy of Sublimation of Ice from Water Clusters?

This short paper reports a study of the electronic dissociation energies, De, of water clusters from direct ab initio (mostly CCSD(T)) calculations and the q-AQUA and MB-pol potentials. These clusters range in size from 6-25 monomers. These are all in very good agreement with each other, as shown in a recent Perspective by Herman and Xantheas. To the best of our knowledge, we present for the first time results for the De per monomer. To our surprise this quantity appears to be converging to a value close to 12 kcal/mol. An estimate of 1.5 - 2 kcal/mol for the {\Delta}ZPE for these clusters puts the value of D0 at 10 to 10.5 kcal/mol. This value is remarkably (and probably fortuitously) close to the reported sublimation enthalpy of 10.2 kcal/mol at 10 K. However, given that these De energies correspond to dissociation of the cluster to N isolated monomers the interpretation of ``vaporization" of these ``solid" clusters is qualitatively reasonable.

physics.chem-ph↗

arXiv2024

Aligning Query Representation with Rewritten Query and Relevance Judgments in Conversational Search

Conversational search supports multi-turn user-system interactions to solve complex information needs. Different from the traditional single-turn ad-hoc search, conversational search encounters a more challenging problem of context-dependent query understanding with the lengthy and long-tail conversational history context. While conversational query rewriting methods leverage explicit rewritten queries to train a rewriting model to transform the context-dependent query into a stand-stone search query, this is usually done without considering the quality of search results. Conversational dense retrieval methods use fine-tuning to improve a pre-trained ad-hoc query encoder, but they are limited by the conversational search data available for training. In this paper, we leverage both rewritten queries and relevance judgments in the conversational search data to train a better query representation model. The key idea is to align the query representation with those of rewritten queries and relevant documents. The proposed model -- Query Representation Alignment Conversational Dense Retriever, QRACDR, is tested on eight datasets, including various settings in conversational search and ad-hoc search. The results demonstrate the strong performance of QRACDR compared with state-of-the-art methods, and confirm the effectiveness of representation alignment.

cs.IR↗

arXiv2024

$\Delta$-Machine Learning to Elevate DFT-based Potentials and a Force Field to the CCSD(T) Level Illustrated for Ethanol

Progress in machine learning has facilitated the development of potentials that offer both the accuracy of first-principles techniques and vast increases in the speed of evaluation. Recently,"$\Delta$-machine learning" has been used to elevate the quality of a potential energy surface (PES) based on low-level, e.g., density functional theory (DFT) energies and gradients to close to the gold-standard coupled cluster level of accuracy. We have demonstrated the success of this approach for molecules, ranging in size from H$_3$O$^+$ to 15-atom acetyl-acetone and tropolone. These were all done using the B3LYP functional. Here we investigate the generality of this approach for the PBE, M06, M06-2X, and PBE0+MBD functionals, using ethanol as the example molecule. Linear regression with permutationally invariant polynomials is used to fit both low-level and correction PESs. These PESs are employed for standard RMSE analysis for training and test datasets, and then general fidelity tests such as energetics of stationary points, normal mode frequencies, and torsional potentials are examined. We achieve similar improvements in all cases. Interestingly, we obtained significant improvement over DFT gradients where coupled cluster gradients were not used to correct the low-level PES. Finally, we present some results for correcting a recent molecular mechanics force field for ethanol and comment on the possible generality of this approach.

physics.chem-ph↗

arXiv2024

ConvSDG: Session Data Generation for Conversational Search

Conversational search provides a more convenient interface for users to search by allowing multi-turn interaction with the search engine. However, the effectiveness of the conversational dense retrieval methods is limited by the scarcity of training data required for their fine-tuning. Thus, generating more training conversational sessions with relevant labels could potentially improve search performance. Based on the promising capabilities of large language models (LLMs) on text generation, we propose ConvSDG, a simple yet effective framework to explore the feasibility of boosting conversational search by using LLM for session data generation. Within this framework, we design dialogue/session-level and query-level data generation with unsupervised and semi-supervised learning, according to the availability of relevance judgments. The generated data are used to fine-tune the conversational dense retriever. Extensive experiments on four widely used datasets demonstrate the effectiveness and broad applicability of our ConvSDG framework compared with several strong baselines.

cs.IR↗

arXiv2024

Tell machine learning potentials what they are needed for: Simulation-oriented training exemplified for glycine

Machine learning potentials (MLPs) are widely applied as an efficient alternative way to represent potential energy surfaces (PES) in many chemical simulations. The MLPs are often evaluated with the root-mean-square errors on the test set drawn from the same distribution as the training data. Here, we systematically investigate the relationship between such test errors and the simulation accuracy with MLPs on an example of a full-dimensional, global PES for the glycine amino acid. Our results show that the errors in the test set do not unambiguously reflect the MLP performance in different simulation tasks such as relative conformer energies, barriers, vibrational levels, and zero-point vibrational energies. We also offer an easily accessible solution for improving the MLP quality in a simulation-oriented manner, yielding the most precise relative conformer energies and barriers. This solution also passed the stringent test by the diffusion Monte Carlo simulations.

physics.chem-ph↗

arXiv2024

Assessing PIP and sGDML Potential Energy Surfaces for H3O2-

Here we assess two machine-learned potentials, one using the symmetric gradient domain machine learning (sGDML) method and one based on permutationally invariant polynomials (PIPs). These are successors to a PIP potential energy surface (PES) reported in 2004. We describe the details of both fitting methods and then compare the two PESs with respect to precision, properties, and speed of evaluation. While the precision of the potentials is similar, the PIP PES is much faster to evaluate for energies and energies plus gradient than the sGDML one. Diffusion Monte Carlo calculations of the ground vibrational state, using both potentials, produce similar large anharmonic downshift of the zero-point energy compared to the harmonic approximation the PIP and sGDML potentials. The computational time for these calculations using the sGDML PES is roughly 300 times greater than using the PIP one.

physics.chem-ph↗

arXiv2024

History-Aware Conversational Dense Retrieval

Conversational search facilitates complex information retrieval by enabling multi-turn interactions between users and the system. Supporting such interactions requires a comprehensive understanding of the conversational inputs to formulate a good search query based on historical information. In particular, the search query should include the relevant information from the previous conversation turns. However, current approaches for conversational dense retrieval primarily rely on fine-tuning a pre-trained ad-hoc retriever using the whole conversational search session, which can be lengthy and noisy. Moreover, existing approaches are limited by the amount of manual supervision signals in the existing datasets. To address the aforementioned issues, we propose a History-Aware Conversational Dense Retrieval (HAConvDR) system, which incorporates two ideas: context-denoised query reformulation and automatic mining of supervision signals based on the actual impact of historical turns. Experiments on two public conversational search datasets demonstrate the improved history modeling capability of HAConvDR, in particular for long conversations with topic shifts.

cs.IR↗

arXiv2024

No Headache for PIPs: A PIP Potential for Aspirin Outperforms Other Machine-Learned Potentials

Assessments of machine-learned (ML) potentials are an important aspect of the rapid development of this field. We recently reported an assessment of the linear-regression permutationally invariant polynomial (PIP) method for ethanol, using the widely used (revised) MD17 dataset. We demonstrated that the PIP approach outperformed numerous other methods, e.g., ANI, PhysNet, sGDML, p-KRR, with respect to precision and notably with respect to speed [Houston $et$ $al$., $J. Chem. Phys.$ 2022, 156, 044120.]. Here we extend this assessment to the 21-atom aspirin molecule, using the rMD17 dataset. Both energies and forces are used for training and the precision of several PIPs is examined for both. Normal mode frequencies, the methyl torsional potential, and 1d vibrational energies for an OH stretch are presented. Overall, we show that the PIPs approach outperforms other ML methods, including sGDML, ANI, GAP, PhysNet, and ACE, as reported by Kov\'acs $et$ $al.$ in $J. Chem. Theory$ $Comput.$ 2021, 17, 7696-7711.

physics.chem-ph↗