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Valay Agarawal

Publications and source records attributed to Valay Agarawal.

12 recordsLinked to original sources

Graph Neural Network Predictions of Carbon 1s Binding Energies with Near-Experimental Accuracy

Graph neural networks are promising architectures for fast, accurate and transferable predictions of core-electron binding energies, which depend on the local bond environment. Here we present a graph neural network model for predicting carbon 1s core-electron binding energies in organic molecules. The model is trained with multiconfiguration pair-density functional theory on 8637 carbon atoms in 2116 molecules with 4-16 atoms and evaluated against 570 experimental values in 113 different molecules containing 3-45 atoms. Previous work benchmarked a mean absolute error of 0.27 eV to experiment for the training data level of theory [J. Phys. Chem. A 2025, 129, 36, 8419-8431] and the present model demonstrates an experimental evaluation error of 0.33 eV with good size transferability to larger organic molecules. An equivariant graph neural network is benchmarked against its rotationally invariant analogue and a model comprised of the smooth overlap of atomic positions descriptors and kernel ridge regression for training data efficiency and stability to non-equilibrium geometries absent from the training data. All models show good training data efficiency and the graph based models have improved transferability to non-equilibrium geometries. The use of chemically informed, graph-normalized node features reduces the graph neural network's dependence on message passing depth. A case study on the 45 atom avobenzone tautomers demonstrates the model's ability for instant and precise analysis of complex molecules. The software and data are provided by the open-source AugerNet package at https://doi.org/10.5281/zenodo.19689244.

physics.chem-ph

Multireference Embedding and Fragmentation Methods for Classical and Quantum Computers: from Model Systems to Realistic Applications

One of the primary challenges in quantum chemistry is the accurate modeling of strong electron correlation. While multireference methods effectively capture such correlation, their steep scaling with system size prohibits their application to large molecules and extended materials. Quantum embedding offers a promising solution by partitioning complex systems into manageable subsystems. In this review, we highlight recent advances in multireference density matrix embedding and localized active space self-consistent field approaches for complex molecules and extended materials. We discuss both classical implementations and the emerging potential of these methods on quantum computers. By extending classical embedding concepts to the quantum landscape, these algorithms have the potential to expand the reach of multireference methods in quantum chemistry and materials.

physics.chem-ph

Enabling Multireference Calculations on Multi-Metallic Systems with Graphic Processing Units

Modeling multimetallic systems efficiently enables faster prediction of desirable chemical properties and design of new materials. This work describes an initial implementation for performing multireference wave function method localized active space self-consistent field (LASSCF) calculations through the use of multiple graphics processing units (GPUs) to accelerate time-to-solution. Density fitting is leveraged to reduce memory requirements, and we demonstrate the ability to fully utilize multi-GPU compute nodes. Performance improvements of 5-10x in total application runtime were observed in LASSCF calculations for multimetallic catalyst systems up to 1200 AOs and an active space of (22e,40o) using up to four NVIDIA A100 GPUs. Written with performance portability in mind, comparable performance is also observed in early runs on the Aurora exascale system using Intel Max Series GPUs.

physics.comp-ph

Pushing the Accuracy Limit of Foundation Neural Network Models with Quantum Monte Carlo Forces and Path Integrals

We propose an end-to-end integrated strategy to produce highly accurate quantum chemistry (QC) synthetic datasets (energies and forces) aimed at deriving Foundation Machine Learning models for molecular simulation. Starting from Density Functional Theory (DFT), a "Jacob's Ladder" approach leverages computationally-optimized layers of massively GPU-accelerated software with increasing accuracy. Thanks to Exascale, this is the first time that the computationally intensive calculation of Quantum Monte Carlo forces (QMC), and the combination of multi-determinant QMC energies and forces with selected-Configuration Interaction wavefunctions, are computed at such scale at the complete basis-set limit. To bridge the gap between accurate QC and condensed-phase Molecular Dynamics, we leverage transfer learning to improve the DFT-based FeNNix-Bio1 foundation model. The resulting approach is coupled to path integrals adaptive sampling quantum dynamics to perform nanosecond reactive simulations at unprecedented accuracy. These results demonstrate the promise of Exascale to deepen our understanding of the inner machinery of complex biosystems.

physics.chem-ph

Distinguishing homolytic versus heterolytic bond dissociation of phenyl sulfonium cations with localized active space methods

Modeling chemical reactions with quantum chemical methods is challenging when the electronic structure varies significantly throughout the reaction, as well as when electronic excited states are involved. Multireference methods such as complete active space self-consistent field (CASSCF) can handle these multiconfigurational situations. However, even if the size of needed active space is affordable, in many cases the active space does not change consistently from reactant to product, causing discontinuities in the potential energy surface. The localized active space SCF (LASSCF) is a cheaper alternative to CASSCF for strongly correlated systems with weakly correlated fragments. The method is used for the first time to study a chemical reaction, namely the bond dissociation of a mono-, di-, and triphenylsulfonium cation. LASSCF calculations generate smooth potential energy scans more easily than the corresponding, more computationally expensive, CASSCF calculations, while predicting similar bond dissociation energies. Our calculations suggest a homolytic bond cleavage for di- and triphenylsulfonium, and a heterolytic pathway for monophenylsulfonium.

physics.chem-ph

Automatic State Interaction with Large Localized Active Spaces for Multimetallic Systems

The localized active space self consistent field (LASSCF) method factorizes a complete active space (CAS) wave function into an antisymmetrized product of localized active space wave function fragments. Correlation between fragments is then reintroduced through LAS state interaction (LASSI), in which the Hamiltonian is diagonalized in a model space of LAS states. However, the optimal procedure for defining the LAS fragments and LASSI model space is unknown. We here present an automated framework to explore systematically convergent sets of model spaces, which we call LASSI[$r$,$q$]. This method requires the user to select only $r$, the number of electron hops from one fragment to another and $q$, the number of fragment basis functions per Hilbert space, which converges to CASCI in the limit of $r,q\to\infty$. Numerical tests of this method on the tri-metal complexes [Fe(III)Al(III)Fe(II)($μ_3$-O)]$^{6+}$ and [Fe(III)$_2$Fe(II)($μ_3$-O)]$^{6+}$ show efficient convergence to the CASCI limit with 4-10 orders of magnitude fewer states.

physics.chem-ph

A Synergistic Approach towards Optimization of Coupled Cluster Amplitudes by Exploiting Dynamical Hierarchy

The coupled cluster iteration scheme for determining the cluster amplitudes involves a set of nonlinearly coupled difference equations. In the space spanned by the amplitudes, the set of equations are analysed as a multivariate time-discrete map where the concept of time appears in an implicit manner. With the observation that the cluster amplitudes have difference in their relaxation timescales with respect to the distributions of their magnitudes, the coupled cluster iteration dynamics are considered as a synergistic motion of coexisting slow and fast relaxing modes, manifesting a dynamical hierarchical structure. With the identification of the highly damped auxiliary amplitudes, their time variation can be neglected compared to the principal amplitudes which take much longer time to reach the fixed points. We analytically establish the adiabatic approximation where each of these auxiliary amplitudes are expressed as unique parametric functions of the collective principal amplitudes, allowing us to study the optimization with the latter taken as the independent degrees of freedom. Such decoupling of the amplitudes significantly reduces the computational scaling without sacrificing the accuracy in the ground state energy as demonstrated by a number of challenging molecular applications. A road-map to treat higher order post-adiabatic effects is also discussed.

physics.comp-ph

Digital quantum simulation of strong correlation effects with iterative quantum phase estimation over the variational quantum eigensolver algorithm: $\mathrm{H_4}$ on a circle as a case study

The iterative quantum phase estimation algorithm, applied to calculating the ground state energies of quantum chemical systems, is theoretically appealing in its wide scope of being able to handle both weakly and strongly correlated regimes. However, the goodness of the initial state that is sent as an input to the algorithm could strongly decide the quality of the results obtained. In this work, we generate the initial state by using the classical-quantum hybrid variational quantum eigensolver algorithm with unitary coupled cluster ansatz. We apply the procedure to obtain the ground state energies of the H4 molecule on a circle, as the system exhibits an interplay of dynamic as well as static correlation effects at different geometries. Furthermore, we argue on the importance of static correlation in construction of the reference determinant, and propose a minimally parametrized unitary coupled cluster ansatz, which drastically reduces number of variational parameters while incorporating the static correlation effects in the wavefunction. We demonstrate that a carefully and appropriately prepared initial state can greatly reduce the effects of noise due to sampling in the estimation of the desired eigenphase.

quant-ph

Assessing the Performance of Nonlinear Regression based Machine Learning Models to Solve Coupled Cluster Theory

The iteration dynamics of the coupled cluster equations exhibits a synergistic relationship among the cluster amplitudes. The iteration scheme may be viewed as a multivariate discrete-time propagation of nonlinearly coupled equations, which is dictated by only a few principal cluster amplitudes. These principal amplitudes usually correspond to only a few valence excitations, whereas all other cluster amplitudes are enslaved, and behave as auxiliary variables. Staring with a few trial iterations, we employ a supervised machine learning strategy to establish a mapping of the principal and auxiliary amplitudes. We introduce a machine learning-coupled cluster hybrid scheme where the coupled cluster equations are solved only to determine the principal amplitudes, which saves significant computation time. The auxiliary amplitudes, on the other hand, are determined via regression. Few different regression techniques have been introduced to express the auxiliary amplitudes as functions of the principal amplitudes. The scheme has been applied to several molecules in their equilibrium and stretched geometries, and our scheme, with both the regression models, shows a significant reduction in computation time without unduly sacrificing the accuracy.

physics.comp-ph

An Approximate Coupled Cluster Theory via Nonlinear Dynamics and Synergetics: the Adiabatic Decoupling Conditions

The coupled cluster iteration scheme is analysed as a multivariate discrete-time map using nonlinear dynamics and synergetics. The nonlinearly coupled set of equations to determine the cluster amplitudes are driven by a fraction of the entire set of the cluster amplitudes. These driver amplitudes enslave all other amplitudes through a synergistic inter-relationship, where the latter class of amplitudes behave as the auxiliary variables. The driver and the auxiliary variables exhibit vastly different time scales of relaxation during the iteration process to reach the fixed points. The fast varying auxiliary amplitudes are small in magnitude, while the driver amplitudes are large, and they have a much longer time scale of relaxation. Exploiting their difference in relaxation time-scale, we employ an adiabatic decoupling approximation, where each of the fast relaxing auxiliary modes are expressed as unique functional of the principal amplitudes. This results in a tremendous reduction in the independent degrees of freedom. On the other hand, only the driver amplitudes are determined accurately via exact coupled cluster equations. We will demonstrate that the iteration scheme has an order of magnitude reduction in computational scaling than the conventional scheme. With a few pilot numerical examples, we would demonstrate that this scheme can achieve very high accuracy with significant savings in computational time.

physics.comp-ph

Accelerating Coupled Cluster Calculations with Nonlinear Dynamics and Shallow Machine Learning

The dynamics associated with the time series of the iteration scheme of coupled cluster theory has been analysed. The phase space analysis indicates the presence of a few significant cluster amplitudes, mostly involving valence excitations, which dictate the dynamics, while all other amplitudes are enslaved. Starting with a few initial iterations to establish the inter-relationship among the cluster amplitudes, a supervised Machine Learning scheme with polynomial Kernel Ridge Regression model has been employed to express each of the enslaved variables uniquely in terms of the master amplitudes. The subsequent coupled cluster iterations are restricted to a reduced dimension only to determine those significant excitations, and the enslaved variables are determined through the already established functional mapping. We will show that our scheme leads to tremendous reduction in computational time without sacrificing the accuracy.

cond-mat.str-el

Stability analysis of a double similarity transformed coupled cluster theory

In this paper, we have analysed the time series associated with the iterative scheme of a double similarity transformed Coupled Cluster theory. The coupled iterative scheme to solve the ground state Schr{ö}dinger equation is cast as a multivariate time-discrete map, the solutions show the universal Feigenbaum dynamics. Using recurrence analysis, it is shown that the dynamics of the iterative process is dictated by a small subgroup of cluster operators, mostly those involving chemically active orbitals, whereas all other cluster operators with smaller amplitudes are enslaved. Using Synergetics, we will indicate how the master-slave dynamics can suitably be exploited to develop a novel coupled-cluster algorithm in a much-reduced dimension.

cond-mat.stat-mech