Coordinate denoising is a promising 3D molecular pre-training method, which has achieved remarkable performance in various downstream drug discovery tasks. Theoretically, the objective is equivalent to learning the force field, which is revealed helpful for downstream tasks. Nevertheless, there are two challenges for coordinate denoising to learn an effective force field, i.e. low coverage samples and isotropic force field. The underlying reason is that molecular distributions assumed by existing denoising methods fail to capture the anisotropic characteristic of molecules. To tackle these challenges, we propose a novel hybrid noise strategy, including noises on both dihedral angel and coordinate. However, denoising such hybrid noise in a traditional way is no more equivalent to learning the force field. Through theoretical deductions, we find that the problem is caused by the dependency of the input conformation for covariance. To this end, we propose to decouple the two types of noise and design a novel fractional denoising method (Frad), which only denoises the latter coordinate part. In this way, Frad enjoys both the merits of sampling more low-energy structures and the force field equivalence. Extensive experiments show the effectiveness of Frad in molecular representation, with a new state-of-the-art on 9 out of 12 tasks of QM9 and on 7 out of 8 targets of MD17.

Ultraviolet spectroscopy provides unique insights into the structure of matter with applications ranging from fundamental tests to photochemistry in the earth's atmosphere and astronomical observations from space telescopes. At longer wavelengths, dual-comb spectroscopy with two interfering laser frequency combs has evolved into a powerful technique that can offer simultaneously a broad spectral range and very high resolution. Here we demonstrate a photon-counting approach that can extend the unique advantages of this method into ultraviolet regions where nonlinear frequency-conversion tends to be very inefficient. Our spectrometer, based on two frequency combs of slightly different repetition frequencies, provides broad span, high resolution, frequency calibration within the accuracy of an atomic clock, and overall consistency of the spectra. We demonstrate a signal-to-noise ratio at the quantum limit and optimal use of the measurement time, provided by the multiplex recording of all spectral data on a single photo-counter. Our initial experiments are performed in the near-ultraviolet and in the visible spectral ranges with alkali-atom vapor, with a power per comb line as low as a femtowatt. This crucial step towards precision broadband spectroscopy at short wavelengths clears the path to extreme-ultraviolet dual-comb spectroscopy and, more generally, generates a new realm of applications for diagnostics at photon level, as encountered e.g., when driving single atoms or molecules.

Mergoassociation of two ultracold atoms to form a weakly bound molecule can occur when two optical traps that each contain a single atom are merged. Molecule formation occurs at an avoided crossing between a molecular state and the lowest motional state of the atom pair. We develop the theory of mergoassociation for pairs of nonidentical nonspherical traps. We develop a coupled-channel approach for the relative motion of the two atoms and present results for pairs of cylindrically symmetrical traps as a function of their anisotropy. We focus on the strength of the avoided crossing responsible for mergoassociation. We also develop an approximate method that gives insight into the dependence of the crossing strength on aspect ratio.

We present an investigation into the transferability of pseudopotentials (PPs) with a nonlinear core correction (NLCC) using the Goedecker, Teter, and Hutter (GTH) protocol across a range of pure GGA, meta-GGA and hybrid functionals, and their impact on thermochemical and non-thermochemical properties. The GTH-NLCC PP for the PBE density functional demonstrates remarkable transferability to the PBE0 and $\omega$B97X-V exchange-correlation functionals, and relative to no NLCC, improves agreement significantly for thermochemical benchmarks compared to all-electron calculations. On the other hand, the B97M-rV meta-GGA functional performs poorly with the PBE-derived GTH-NLCC PP, which is mitigated by reoptimizing the NLCC parameters for this specific functional. The findings reveal that atomization energies exhibit the greatest improvements from use of the NLCC, which thus provides an important correction needed for covalent interactions relevant to applications involving chemical reactivity. Finally we test the NLCC-GTH PPs when combined with medium-size TZV2P molecularly optimized (MOLOPT) basis sets which are typically utilized in condensed phase simulations, and show that they lead to consistently good results when compared to all-electron calculations for atomization energies, ionization potentials, barrier heights, and non-covalent interactions, but lead to somewhat larger errors for electron affinities.

Herein, NiO nanosheets supported with Ag single atoms are synthesized for photothermal CO2 hydrogenation to achieve 1065 mmol g-1 h-1 of CO production rate under 1 sun irradiation, revealing the unparalleled weak sunlight driven reverse water-gas shift reaction (RWGS) activity. This performance is attributed to the coupling effect of Ag-O-Ni sites to enhance the hydrogenation of CO2 and weaken the CO adsorption, resulting in 1434 mmol g-1 h-1 of CO yield at 300 degree, surpassing any low-temperature RWGS performances ever reported. Building on this, we integrated the 2D Ni1Ag0.02O1 supported photothermal RWGS with commercial photovoltaic electrolytic water splitting, leading to the realization of 103 m2 scale artificial photosynthesis system with a daily CO yield of 18.70 m3, a photochemical energy conversion efficiency of >16%, over 90% H2 ultilazation efficiency, outperforming other types of artificial photosynthesis. The results of this research chart a promising course for designing practical, natural sunlight-driven artificial photosynthesis systems and highly efficient platinum-free CO2 hydrogenation catalysts. This work is a significant step towards harnessing solar energy more efficiently and sustainably, opening exciting possibilities for future research and development in this area.

Experimental and theoretical results about entropy limits for macroscopic and single-particle systems are reviewed. It is clarified when it is possible to speak about a quantum of entropy, given by the Boltzmann constant k, and about a lower entropy limit $S \geq k \ln 2$. Conceptual tensions with the third law of thermodynamics and the additivity of entropy are resolved. Black hole entropy is also surveyed. Further claims for vanishing entropy values are shown to contradict the requirement of observability, which, as possibly argued for the first time, also implies $S \geq k \ln 2$. The uncertainty relations involving the Boltzmann constant and the possibility of deriving thermodynamics from the existence of a quantum of entropy enable one to speak about a principle of the entropy limit that is valid across nature.

We introduce an efficient and robust method to compute alchemical free energy differences, resulting from the application of multiple walker Adaptive Biasing Force (ABF) in conjunction with strongly damped Langevin $\lambda$-dynamics. Unbiased alchemical free energy surfaces are naturally recovered by Thermodynamic Integration (TI). No manual optimization of the $\lambda$ schedule is required as the sampling of the $\lambda$ variable is continuous and converges towards a uniform distribution. Free diffusion of $\lambda$ improves orthogonal relaxation compared to fixed $\lambda$ methods such as standard TI or Free Energy Perturbation (FEP). Furthermore, the multiple walker strategy provides coverage of orthogonal space in a generic way with minimal user input and negligible computational overhead. Of practical importance, no adiabatic decoupling between the alchemical and Cartesian degrees of freedom is assumed, ensuring unbiased estimates for a wide envelope of numerical parameters. We present two high-performance implementations of the method in production molecular dynamics engines, namely NAMD and Tinker-HP, through coupling with the Colvars open source library. These interfaces enable the combination of the rich feature sets of those packages. We demonstrate the correctness and efficiency of the approach on several real-world cases: from solvation free energies up to ligand-receptor binding (using a recently proposed binding restraint scheme) with both fixed-charge and polarizable models. We find that, for a chosen accuracy, the computational cost is strongly reduced compared to state-of-the-art fixed-lambda methods and that results within 1~kcal/mol of experimental value are recovered for the most complex system. The implementation is publicly available and readily usable by practitioners of current alchemical methods.

A new synchrotron study for CH$_2$F$_2$ from has been combined with earlier data. The onset of absorption, band I and also band IV, is resolved into broad vibrational peaks, which contrast with the continuous absorption previously claimed. A new theoretical analysis, using a combination of time dependent density functional theory (TDDFT) calculations and complete active space self-consistent field, leads to a major new interpretation. Adiabatic excitation energies (AEEs) and vertical excitation energies, evaluated by these methods, are used to interpret the spectra in unprecedented detail using theoretical vibronic analysis. This includes both Franck-Condon (FC) and Herzberg-Teller (HT) effects on cold and hot bands. These results lead to the re-assignment of several known excited states and the identification of new ones. The lowest calculated AEE sequence for singlet states is 1$^1$B$_1$ $\sim$ 1$^1$A$_2$ < 2$^1$B$_1$ < 1$^1$A$_1$ < 2$^1$A$_1$ < 1$^1$B$_2$ < 3$^1$A$_1$ < 3$^1$B$_1$. These, together with calculated higher energy states, give a satisfactory account of the principal maxima observed in the VUV spectrum. Basis sets up to quadruple zeta valence with extensive polarization are used. The diffuse functions within this type of basis generate both valence and low-lying Rydberg excited states. The optimum position for the site of further diffuse functions in the calculations of Rydberg states is shown to lie on the H-atoms. The routine choice on the F-atoms is shown to be inadequate for both CHF$_3$ and CH$_2$F$_2$. The lowest excitation energy region has mixed valence and Rydberg character. TDDFT calculations show that the unusual structure of the onset arises from the near degeneracy of 1$^1$B$_1$ and 1$^1$A$_2$ valence states, which mix in symmetric and antisymmetric combinations.

We derive a widely-applicable first principles approach for determining two-body, static effective interactions for low-energy Hamiltonians with quantitative accuracy. The algebraic construction rigorously conserves all instantaneous two-point correlation functions in a chosen model space at the level of the random phase approximation, improving upon the traditional uncontrolled static approximations. Applied to screened interactions within a quantum embedding framework, we demonstrate these faithfully describe the relaxation of local subspaces via downfolding high-energy physics in molecular systems, as well as enabling a systematically improvable description of the long-range plasmonic contributions in extended graphene.

We demonstrate a novel single molecule technique that is compatible with high precision measurements and obtain the spectrum of two molecular ion species. While the current result yields modest spectral resolution due to a broad light source, we expect the method to ultimately provide resolution comparable to quantum logic methods with significantly less stringent requirements. Adaptations of this technique will prove useful in a wide range of precision spectroscopy arenas including the search for parity violating effects in chiral molecules.

Multiferroic CoFe2O4-Ba0.95Ca0.05Ti0.89Sn0.11O3 core-shell nanofibers (CFO@BCTSn NFs) were synthesized by a sol-gel co-axial electrospinning technique. The scanning electron microscope and transmission electron microscope were used to check nanofibers' core-shell structure/configuration. X-ray diffraction and a high-resolution transmission electron microscope were used to confirm the spinel structure of CFO and the perovskite structure of BCTSn. The magnetic character of the resultant CFO@BCTSn NFs was determined by SQUID magnetometry. The piezoelectricity was verified using piezo-response force microscopy, which revealed an entirely covered ferroelectric shell outline, in accordance with SEM and TEM observations. The magnetoelectric (ME) coefficient was measured as a function of the applied external DC magnetic field. The maximum ME coefficient obtained for the CFO@BCTSn NFs was 346 mV cm-1 Oe-1. The high magnetoelectric coupling suggests that CFO@BCTSn NFs could be a promising candidate for magnetic field sensor and magnetoelectric device applications.

Synthetic nanomotors powered by chemical reactions have been designed to act as vehicles for active cargo transport, drug delivery as well as a variety of other uses. Collections of such motors, acting in consort, can self-assemble to form swarms or clusters, providing opportunities for applications on various length scales. While such collective behavior has been studied when the motors move in a chemically inactive fluid environment, when the medium in which they move is a chemical network that supports complex spatial and temporal patterns we show that collective behavior changes. Spatial patterns in the environment can guide and control motor collective states, and interactions of the motors with their environment can give rise to distinctive spatiotemporal motor patterns. The results are illustrated by studies of the motor dynamics in systems that support Turing patterns and spiral waves. This work is relevant for potential applications that involve many active nanomotors moving in complex chemical or biological environments.

We present the development and implementation of the relativistic coupled cluster linear response theory (CC-LR) which allows the determination of molecular properties arising from time-dependent or time-independent electric, magnetic, or mixed electric-magnetic perturbations (within a common gauge origin), and take into account the finite lifetime of excited states via damped response theory. We showcase our implementation, which is capable to offload intensive tensor contractions onto graphical processing units (GPUs), in the calculation of: \textit{(a)} frequency-(in)dependent dipole-dipole polarizabilities of IIB atoms and selected diatomic molecules, with a emphasis on the calculation of valence absorption cross-sections for the I$_2$ molecule;\textit{(b)} indirect spin-spin coupling constants for benchmark systems such as the hydrogen halides (HX, X = F-I) as well the H$_2$Se-H$_2$O dimer as a prototypical system containing hydrogen bonds; and \textit{(c)} optical rotations at the sodium D line for hydrogen peroxide analogues (H$_{2}$Y$_{2}$, Y=O, S, Se, Te). Thanks to this implementation, we are able show the similarities in performance--but often the significant discrepancies--between CC-LR and approximate methods such as density functional theory (DFT). Comparing standard CC response theory with the equation of motion formalism, we find that, for valence properties such as polarizabilities, the two frameworks yield very similar results across the periodic table as found elsewhere in the literature; for properties that probe the core region such as spin-spin couplings, we show a progressive differentiation between the two as relativistic effects become more important. Our results also suggest that as one goes down the periodic table it may become increasingly difficult to measure pure optical rotation at the sodium D line, due to the appearance of absorbing states.

How does an electrochemical interface respond to changes in the electrode potential? How does the response affect the key properties of the system - energetics, excess charge, capacitance? Essential questions key to ab-initio simulations of electrochemical systems, which we address in this work on the basis of a rigorous mathematical evaluation of the interfacial energetics at constant applied potential. By explicitly taking into account the configurational and electronic degrees of freedom we derive important statements about stationary points in the electronically grand canonical ensemble. We analyze their geometric response to changes in electrode potential and show that it can be mapped identically onto an additional contribution to the system's capacitance. We draw similar conclusions for the constant charge ensemble which equally allows to assess the respective stationary points. Our analysis of the relation between the canonical and grand canonical energetics reveals, however, one key difference between both ensembles. While the constant potential ensemble yields in general positive capacitances at local minima, the capacitance of local minima in the constant charge ensemble might become negative. We trace back this feature to the possibility of character switching of stationary points when switching between the ensembles causing the differences in the response to perturbations. Our systematical analysis not only provides a detailed qualitative and quantitative understanding of the interplay between electronic and configurational degrees of freedom and their contributions to the energetics of electrified interfaces but also highlights the similarities and subtle dissimilarities between the canonical and grand canonical description of the electronic degrees of freedom, which is crucial for a better understanding of theoretical calculations with and without potentiostat.

We introduce a machine-learning approach (denoted Symmetry Seeker Neural Network) capable of automatically discovering discrete symmetry groups in physical systems. This method identifies the finite set of parameter transformations that preserve the system's physical properties. Remarkably, the method accomplishes this without prior knowledge of the system's symmetry or the mathematical relationships between parameters and properties. Demonstrating its versatility, we showcase examples from mathematics, nanophotonics, and quantum chemistry.

We present the first experimental application of coherent Raman spectroscopy (CRS) on the ro-vibrational $\nu_2$ mode spectrum of methane (CH$_4$). Ultrabroadband femtosecond/picosecond (fs/ps) CRS is performed in the molecular fingerprint region from 1100 to 2000 cm$^{-1}$, employing fs laser-induced filamentation as the supercontinuum generation mechanism to provide the ultrabroadband excitation pulses. We introduce a time-domain model of the CH$_4$ $\nu_2$ CRS spectrum, including all five ro-vibrational branches allowed by the selection rules $\Delta v = 1$, $\Delta J = 0$, $\pm1$, $\pm2$; the model includes collisional linewidths, computed according to a modified exponential gap scaling law and validated experimentally. The use of ultrabroadband CRS for in situ monitoring of the CH$_4$ chemistry is demonstrated in a laboratory CH$_4$/air diffusion flame: CRS measurements in the fingerprint region, performed across the laminar flame front, allow the simultaneous detection of molecular oxygen (O$_2$), carbon dioxide (CO$_2$), and molecular hydrogen (H$_2$), along with CH$_4$. Fundamental physicochemical processes, such as H$_2$ production via CH$_4$ pyrolysis, are observed through the Raman spectra of these chemical species. In addition, we demonstrate ro-vibrational CH$_4\nu_2$ CRS thermometry, and we validate it against CO$_2$ CRS measurements. The present technique offers an interesting diagnostics approach to in situ measurement of CH$_4$-rich environments, e.g., in plasma reactors for CH$_4$ pyrolysis and H$_2$ production.

In this work, we present a general machine learning approach for full-dimensional potential energy surfaces for tetra-atomic systems. Our method employs an active learning scheme trained on {\it ab initio} points, which size grows based on the accuracy required. The training points are selected based on molecular dynamics simulations, choosing the most suitable configurations for different collision energy and mapping the most relevant part of the potential energy landscape of the system. The present approach does not require long-range information and is entirely general. As an example, we provide the full-dimensional AlF-AlF potential energy surface, requiring $\lesssim 0.1\%$ of the configurations to be calculated {\it ab initio}. Furthermore, we analyze the general properties of the AlF-AlF system, finding key difference with other reported results on CaF or bi-alkali dimers.

Strong cavity coupling of gas-phase molecules will enable studies of benchmark chemical processes under strong light-matter interactions with a high level of experimental control and no solvent effects. We recently demonstrated the formation of gas-phase molecular polaritons by strongly coupling a bright rovibrational transition of methane to a Fabry-P\'erot optical cavity mode inside a cryogenic buffer gas cell. Here, we further explore the flexible capabilities of this infrastructure. We show that we can greatly increase the collective coupling strength of the molecular ensemble to the cavity by increasing the intracavity methane number density. In doing so, we access a multimode coupling regime in which many nested polaritonic states arise as the Rabi splitting approaches the cavity mode spacing. We explore polariton formation for cavity geometries of varying length, finesse, and mirror radius of curvature. We also report a proof-of-principle demonstration of rovibrational gas-phase polariton formation at room temperature. This experimental flexibility affords a great degree of control over the properties of molecular polaritons and opens up a wider range of simple molecular processes to future interrogation under strong cavity-coupling. We anticipate that ongoing work in gas-phase polaritonics will facilitate convergence between experimental results and theoretical models of cavity-altered chemistry and physics.

Density functional theory (DFT) is widely used to predict chemical properties, but its accuracy is limited by functional approximations and their approximate self-consistent densities. Density-corrected DFT (DC-DFT) is the study of the errors due to densities and Hartree-Fock DFT (HF-DFT) uses HF densities to improve energetics. With increasing use of HF-DFT, the question of how to address strong spin contamination in the HF calculation becomes increasingly important. We compare two different open-shell HF densities across 13 different DFT functionals and two DC-DFT methods. For significant spin contamination, ROHF densities outperform UHF densities by as much as a factor of 3, depending on the energy functional, and ROHF-DFT improves over self-consistent DFT for most of the tested functionals. We refine the DC(HF)-DFT algorithm, recommending ROHF-DFT in cases of severe spin contamination.

Accurate solutions to the electronic Schr\"odinger equation can provide valuable insight for electron interactions within molecular systems, accelerating the molecular design and discovery processes in many different applications. However, the availability of such accurate solutions are limited to small molecular systems due to both the extremely high computational complexity and the challenge of operating and executing these workloads on high-performance compute clusters. This work presents a massively scalable cloud-based quantum chemistry platform by implementing a highly parallelizable quantum chemistry method that provides a polynomial-scaling approximation to full configuration interaction (FCI). Our platform orchestrates more than one million virtual CPUs on the cloud to analyze the bond-breaking behaviour of carbon-fluoride bonds of per- and polyfluoroalkyl substances (PFAS) with near-exact accuracy within the chosen basis set. This is the first quantum chemistry calculation utilizing more than one million virtual CPUs on the cloud and is the most accurate electronic structure computation of PFAS bond breaking to date.