Polynomial Invariants Research Articles

Polynomial Invariants for Rooted Trees Related to Their Random Destruction

We consider three bivariate polynomial invariants $P$, $A$, and $S$ for rooted trees, as well as a trivariate polynomial invariant $M$. These invariants are motivated by random destruction processes such as the random cutting model or site percolation on rooted trees. We exhibit recursion formulas for the invariants and identities relating $P$, $S$, and $M$. The main result states that the invariants $P$ and $S$ are complete, that is they distinguish rooted trees (in fact, even rooted forests) up to isomorphism. The proof method relies on the obtained recursion formulas and on irreducibility of the polynomials in suitable unique factorization domains. For $A$, we provide counterexamples showing that it is not complete, although that question remains open for the trivariate invariant $M$.

On Knots with Cyclic Symmetries

This review paper investigates the relationship between symmetries of knots and links in the three-dimensional sphere, with a focus on cyclic symmetries, and their associated polynomial invariants. It examines the behavior of these polynomials in the case where the knot is set-wise fixed by the action of finite cyclic group on the 3-sphere. The study highlights how these invariants can obstruct the existence of such symmetries, providing valuable insights into the topological properties of these knots. The paper reviews established results on polynomial criteria for periodicity and their extensions to freely periodic links. It also explores generalizations to study the symmetries of virtual knots and spatial graphs.

Free Reflection Multiarrangements and Quasi-Invariants

Abstract To a complex reflection arrangement with an invariant multiplicity function one can relate the space of logarithmic vector fields and the space of quasi-invariants, which are both modules over invariant polynomials. We establish a close relation between these modules. Berest–Chalykh freeness results for the module of quasi-invariants lead to new free complex reflection multiarrangements. Saito’s primitive derivative gives a linear map between certain spaces of quasi-invariants. We also establish a close relation between non-homogeneous quasi-invariants for root systems and logarithmic vector fields for the extended Catalan arrangements. As an application, we prove the freeness of Catalan arrangements corresponding to the non-reduced root system $BC_{N}$.

DFT-Based Permutationally Invariant Polynomial Potentials Capture the Twists and Turns of C14H30.

Hydrocarbons are ubiquitous as fuels, solvents, lubricants, and as the principal components of plastics and fibers, yet our ability to predict their dynamical properties is limited to force-field mechanics. Here, we report two machine-learned potential energy surfaces (PESs) for the linear 44-atom hydrocarbon C14H30 using an extensive data set of roughly 250,000 density functional theory (DFT) (B3LYP) energies for a large variety of configurations, obtained using MM3 direct-dynamics calculations at 500, 1000, and 2500 K. The surfaces, based on Permutationally Invariant Polynomials (PIPs) and using both a many-body expansion approach and a fragmented-basis approach, produce precise fits for energies and forces and also produce excellent out-of-sample agreement with direct DFT calculations for torsional and dihedral angle potentials. Going beyond precision, the PESs are used in molecular dynamics calculations that demonstrate the robustness of the PESs for a large range of conformations. The many-body PIPs PES, although more compute intensive than the fragmented-basis one, is directly transferable for other linear hydrocarbons.

Δ-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, Δ-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 H3O+ 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 data sets, 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.

COMPUTING THE DEGREE-4 INVARIANT POLYNOMIAL BASIS FOR 7 QUBITS

Understanding the complexity of entangled states within the context of SLOCC (stochastic local operations and classical communications) involving several number qubits is essential for advancing our knowledge of quantum systems. This complexity is often analyzed by classifying the states via local symmetry groups. Practically, tthe resulting classes can be distinguished using invariant polynomials, but the size of these polynomials grows rapidly. Hence, it is crucial to obtain the smallest possible invariants. In this short note, we compute the basis of invariant polynomials of 7 qubits of degree 4, which are the smallest degree invariants. We obtain these polynomials using the representation theory and algebraic combinatorics.

Chromatic symmetric functions and polynomial invariants of trees

AbstractStanley asked whether a tree is determined up to isomorphism by its chromatic symmetric function. We approach Stanley's problem by studying the relationship between the chromatic symmetric function and other invariants. First, we prove Crew's conjecture that the chromatic symmetric function of a tree determines its generalized degree sequence, which enumerates vertex subsets by cardinality and the numbers of internal and external edges. Second, we prove that the restriction of the generalized degree sequence to subtrees contains exactly the same information as the subtree polynomial, which enumerates subtrees by cardinality and number of leaves. Third, we construct arbitrarily large families of trees sharing the same subtree polynomial, proving and generalizing a conjecture of Eisenstat and Gordon.

A Low-Order Permutationally Invariant Polynomial Approach to Learning Potential Energy Surfaces Using the Bond-Order Charge-Density Matrix: Application to Cn Clusters for n = 3-10, 20.

A representation for learning potential energy surfaces (PESs) in terms of permutationally invariant polynomials (PIPs) using the Hartree-Fock expression for electronic energy is proposed. Our approach is based on the one-electron core Hamiltonian weighted by the configuration-dependent elements of the bond-order charge density matrix (CDM). While the previously reported model used an s-function Gaussian basis for the CDM, the present formulation is expanded with p-functions, which are crucial for describing chemical bonding. Detailed results are demonstrated on linear and cyclic Cn clusters (n = 3-10) trained on extensive B3LYP/aug-cc-pVTZ data. The described method facilitates PES learning by reducing the root mean squared error (RMSE) by a factor of 5 relative to the s-function formulation and by a factor of 20 relative to the conventional PIP approach. This is equivalent to using CDM and an sp basis with a PIP of order M to achieve the same RMSE as with the conventional method with a PIP of order M + 2. Implications for large-scale problems are discussed using the case of the PES of the C20 fullerene in full permutational symmetry.

Dynamics of the Cl + CH3CN reaction on an automatically-developed full-dimensional abinitio potential energy surface.

A full-dimensional analytical potential energy surface (PES) is developed for the Cl + CH3CN reaction following our previous work on the benchmark abinitio characterization of the stationary points. The spin-orbit-corrected PES is constructed using the Robosurfer program and a fifth-order permutationally invariant polynomial method for fitting the high-accuracy energy points determined by a ManyHF-based coupled-cluster/triple-zeta-quality composite method. Quasi-classical trajectory simulations are performed at six collision energies between 10 and 60kcal mol-1. Multiple low-probability product channels are found, including isomerization to isonitrile (CH3NC), but out of the eight possible channels, only the H-abstraction has significant reaction probability; thus, detailed dynamics studies are carried out only for this reaction. The cross sections and opacity functions show that the probability of the H-abstraction reaction increases with increasing collision energy (Ecoll). Scattering angle, initial attack angle, and product relative translational energy distributions indicate that the mechanism changes with the collision energy from indirect/rebound to direct stripping. The distribution of initial attack angles shows a clear preference for methyl group attack but with different angles at different Ecoll values. Post-reaction energy distributions show that the energy transfer is biased toward the products' relative translational energy instead of their internal energy. Rotational and vibrational energy have about the same amount of contribution to the internal energy in the case of both products (HCl and CH2CN), i.e., both of them are formed with high rotational excitations. HCl is produced mostly in the ground vibrational state, while a notable fraction of CH2CN is formed with vibrational excitation.

Graded picture invariants and polynomial invariants for mixed tensor superspaces

In this paper we consider the mixed tensor space of a Z2-graded vector space. We obtain a spanning set of invariants of the associated symmetric algebra under the action of the general linear supergroup as well as the queer supergroup over the Grassmann algebra. As a consequence, we give a generating set of polynomial invariants for the simultaneous adjoint action of the general linear supergroup on several copies of its Lie superalgebra. We show that in this special case, this set turns out to be the set of supertrace monomials, which is analogous to the result of Procesi for the general linear group. A queer supergroup analogue of these results is also obtained.

Fundamental Invariant Neural Network (FI-NN) Potential Energy Surface for the OH + CH3OH Reaction with Analytical Forces.

The hydrogen abstraction reaction of OH + CH3OH plays a great role in combustion and atmospheric and interstellar chemistry and has been extensively studied theoretically and experimentally. Theoretically, the numerical gradients with respect to the Cartesian coordinates of atoms in molecular simulations on our recent potential energy surface (PES) for the title reaction trained using the permutationally invariant polynomial neural network (PIP-NN) approach hinder the extensive calculation because of the unaffordable computation cost. To address this issue, we in this work report a new full-dimensional accurate analytical PES for the title reaction using the fundamental invariant neural network (FI-NN) approach based on 140,192 points of the quality UCCSD(T)-F12a/AVTZ. Besides, the spin-orbit (SO) corrections of OH in the entrance channel were determined at the level of complete active space self-consistent field with the AVTZ basis set. As a compromise between computational cost and efficiency, the Δ-machine learning approach was employed to construct the SO-corrected PES. Based on this new FI-NN PES with analytical forces, thermal rate coefficients and various dynamic properties, including the integral cross sections, the differential cross sections, and the product energy partitioning, were determined by running a total of 5.5 million trajectories. The use of analytical gradients of the FI-NN PES accelerated simulations and about 99% of computation cost was saved, compared to that for the PIP-NN PES with numerical gradients. Such a significant acceleration is achieved mainly by replacing PIPs with FIs.

High-Energy Reaction Dynamics of N3.

The atom-exchange and atomization dissociation dynamics for the N(4S) + N2(1Σg+) reaction are studied using a reproducing kernel Hilbert space (RKHS)-based, global potential energy surface (PES) at the MRCI-F12/aug-cc-pVTZ-F12 level of theory (MRCI, multireference configuration interaction). For the atom exchange reaction (NANB + NC → NANC + NB), computed thermal rates and their temperature dependence from quasi-classical trajectory (QCT) simulations agree to within error bars with the available experiments. Companion QCT simulations using a recently published CASPT2-based PES confirm these findings. For the atomization reaction, leading to three N(4S) atoms, the computed rates from the RKHS-PES overestimate the experimentally reported rates by 1 order of magnitude, whereas those from the permutationally invariant polynomial (PIP)-PES agree favorably, and the T dependence of both computations is consistent with the experiment. These differences can be traced back to the different methods and basis sets used. The lifetime of the metastable N3 molecule is estimated to be ∼200 fs depending on the initial state of the reactants. Finally, neural-network-based exhaustive state-to-distribution models are presented using both PESs for the atom exchange reaction. These models will be instrumental for a broader exploration of the reaction dynamics of air.

Maximal Amplitudes of Hyperelliptic Solutions of the Modified Nonlinear Schrödinger Equation

A simple formula is proven for the maximal amplitudes of N-phase hyperelliptic solutions of the modified nonlinear Schrödinger equation. The simple formula for the maximal amplitude depends only on the roots of an invariant polynomial.

A Neural Network Potential Energy Surface and Quantum Dynamics Study of Ca(1S) + H2(v 0 = 0, j 0 = 0) → CaH + H Reaction.

The reactive collision between Ca and H2 molecules has attracted great interest experimentally due to the key role of the product CaH molecule in the field of astrophysics and cold molecules. However, quantum dynamics calculations for this system have not been reported due to the lack of a global potential energy surface (PES). Herein, a globally accurate PES of the ground-state CaH2 is developed by combining 11365 high-level ab initio points and permutation invariant polynomial neural network method. Based on the newly constructed PES, the state-to-state quantum dynamics calculations for the Ca(1S) + H2 (v 0 = 0, j 0 = 0) → CaH + H reaction are carried out using the time-dependent wave packet method. The dynamic results reveal that the reaction follows the complex-forming mechanism near the reactive threshold, whereas both the indirect insertion mechanism and direct abstraction mechanism have effects at higher collision energies. The newly constructed PES can be used to further study the influence of isotope substitution, rovibrational excitation, and spatial orientation of reactant molecules on reaction dynamics.

Theoretical Study of the Thermal Rate Coefficients of the H3+ + C2H4 Reaction: Dynamics Study on a Full-Dimensional Potential Energy Surface.

Ion-molecular reactions play a significant role in molecular evolution within the interstellar medium. In this study, the entrance channel reaction, H3+ + C2H4 → H2 + C2H5+, was investigated using classical molecular dynamic (classical MD) and ring polymer molecular dynamic (RPMD) simulation techniques. We developed an analytical potential energy surface function with a permutationally invariant polynomial basis, specifically employing the monomial symmetrized approach. Our dynamic simulations reproduced the rate coefficient of 300 K for H3+ + C2H4 → H2 + C2H5+, aligning reasonably well with the values in the kinetic database commonly utilized in astrochemistry. The thermal rate coefficients obtained using both the classical MD and RPMD techniques exhibited an increase from 100 K to 300 K as the temperature rose. Additionally, we analyzed the excess energy distribution of the C2H5+ fragment with respect to temperature to investigate the indirect reaction pathway of C2H5+ → H2 + C2H3+. This result suggests that the indirect reaction pathway of C2H5+ → H2 + C2H3+ holds minor significance, although the distribution highly depends on the collisional temperature.

(Un)Solvable loop analysis

AbstractAutomatically generating invariants, key to computer-aided analysis of probabilistic and deterministic programs and compiler optimisation, is a challenging open problem. Whilst the problem is in general undecidable, the goal is settled for restricted classes of loops. For the class of solvable loops, introduced by Rodríguez-Carbonell and Kapur (in: Proceedings of the ISSAC, pp 266–273, 2004), one can automatically compute invariants from closed-form solutions of recurrence equations that model the loop behaviour. In this paper we establish a technique for invariant synthesis for loops that are not solvable, termed unsolvable loops. Our approach automatically partitions the program variables and identifies the so-called defective variables that characterise unsolvability. Herein we consider the following two applications. First, we present a novel technique that automatically synthesises polynomials from defective monomials, that admit closed-form solutions and thus lead to polynomial loop invariants. Second, given an unsolvable loop, we synthesise solvable loops with the following property: the invariant polynomials of the solvable loops are all invariants of the given unsolvable loop. Our implementation and experiments demonstrate both the feasibility and applicability of our approach to both deterministic and probabilistic programs.

Superconformal anomalies from superconformal Chern-Simons polynomials

We consider the 4-dimensional N\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$ \\mathcal{N} $$\\end{document} = 1 Lie superconformal algebra and search for completely “symmetric” (in the graded sense) 3-index invariant tensors. The solution we find is unique and we show that the corresponding invariant polynomial cubic in the generalized curvatures of superconformal gravity vanishes. Consequently, the associated Chern-Simons polynomial is a non-trivial anomaly cocycle. We explicitly compute this cocycle to all orders in the independent fields of superconformal gravity and establish that it is BRST equivalent to the so-called superconformal a-anomaly. We briefly discuss the possibility that the superconformal c-anomaly also admits a similar Chern-Simons formulation and the potential holographic, 5-dimensional, interpretation of our results.

Quantum Monte Carlo Simulations of the Vibrational Wavefunction of the Aromatic Cyclo[10]carbon Using a Full Dimensional Permutationally Invariant Potential Energy Surface.

New experimental measurements [Sun et al., Nature 2023, 623, 972] of the cyclic C10 reveal a cumulenic pentagon-like D5h structure at ∼5 K. However, the long-standing presumption that a large zero-point vibrational energy combined with an extremely flat D5h ↔ D10h ↔ D5h isomerization pathway washes out the pentagonal D5h structure and yields a symmetric D10h decagon remains at odds with the experiment. We resolve this issue with our fitting approach based on a bond-order charge-density matrix expressed in permutationally invariant polynomials. We train the model on τHCTH/cc-pVQZ data morphed to reproduce a relativistic all-electron CCSDT(Q)/CBS D5h-D10h potential energy barrier (benchmarked previously by others). Large scale diffusion Monte Carlo simulations in full dimensionality show that the vibrational ground state of C10 has compositional character of more than 96% D5h, fully reflecting the experimental imaging data. Quantum mechanical variational calculations in 1-D further suggest persistence of the D5h symmetry structure at higher temperatures.

Accurate neural-network-based fitting of full-dimensional N2 –Ar and N2–CH4 two-body potential energy surfaces aimed at spectral simulations

We describe the development of machine-learned (ML) potentials for flexible, weakly interacting monomers. A recently suggested permutationally invariant polynomial neural network (PIP-NN) approach is utilised to represent the full-dimensional two-body component of the molecular pair energy. To ensure the asymptotic zero-interaction limit, a tailored subset of the full invariant polynomial basis set is utilised, and their variables are modified to achieve a better fit of the correct asymptotic behaviour at a long range. This new technique is used to build full-dimensional potentials for the two-body N 2 –Ar and N 2 –CH 4 interactions by fitting databases of ab initio energies calculated at the coupled-cluster level of theory. The second virial coefficient, fully accounting for molecular flexibility, is then calculated within the classical framework using the obtained PIP-NN potential surfaces. A trajectory-based simulation of the N 2 –Ar collision-induced absorption is conducted, covering both the far- and mid-infrared ranges.

Global Potential Energy Surfaces by Compressed-State Multistate Pair-Density Functional Theory for Hyperthermal Collisions in the O2+O2 System.

Interactions between oxygen molecules play an important role in atmospheric chemistry and hypersonic flow chemistry in atmospheric entries. Recently, high-quality ab initio potential energy surface (PES) of the quintet O4 was reported by Paukku et al. [J. Chem. Phys. 147, 034301 (2017)]. 10543 configurations were sampled and calculated at the level of MS-CASPT2/maug-cc-pVTZ with scaled external correlation. The PES was fitted to a many-body (MB) form with the many-body part described by the permutationally invariant polynomial approach (MB-PIP). In this work, the PIP-Neural Network (PIP-NN) and MB-PIP-NN methods were used to refit the PES based on the same data by Paukku et al. Three PESs were compared. It was found that the performances differ significantly in the O+O3 region as well as in the long-range region. Therefore, additional 1300 points were sampled, and the efficient compressed-state multistate pair-density functional theory (CMS-PDFT) was used to calculate the electronic structure of these 1300 points and 10543 points by Paukku et al. Then, a completely new quintet PES was fitted using the MB-PIP-NN method. Based on this PES, the quasi-classical trajectory (QCT) approach was used to reveal all possible reaction channels for hyperthermal O2-O2 collisions.