arXiv subjects

Daniel Peláez

Publications and source records attributed to Daniel Peláez.

8 recordsLinked to original sources

arXiv2026

Variational computation of anharmonic ground and excited vibrational eigenstates using bound Quartic Force Fields: Application with MCTDH and ElVibRot

In this work we introduce the use of Quartic Force fields (QFF) potential expansions in the context of variational calculations. Such potentials are commonly employed in molecular Vibrational Second-Order Perturbation Theory (VPT2) studies, for which equations explicitly dependent on the QFF parameters exist. However, QFF are unbound potentials for more or less large displacements from the reference point and, most of the time, this prevents their use in conjunction with variational wavepacket-based calculations. In this work, we propose a general correction to QFFs and introduce a fully automated numerical approach to avoid their unbound character. Our corrected potentials, bound QFF (bQFF), do not exhibit appreciable modification of the local topography around the region of interest for infrared spectroscopy. As a consequence of this, we can affirm that the vibrational eigenstructure (eigenvalues, eigenstates) remains essentially unaltered by our correction. To illustrate their numerical stability, we have interfaced our bQFF routines in combination with to two well-established quantum simulation software packages MCTDH and \textsc{ElVibRot} which feature variational approaches. More specifically, our bQFFs are separable and hence directly expressible as MCTDH operators. Furthermore, concerning the size of our bQFF expansion, we show that it is possible to tensor-decompose our bQFF in Canonical Polyadic form (CP-bQFF). We use the Monte Carlo Canonical Polyadic decomposition algorithm for this. CP-bQFF results are virtually identical to uncompressed bQFF, but the computational efficiency is largely improved. Our approach paves the way for the automated variational study of anharmonic eigenstates in molecular systems within the reach of QFF-based potentials, using either time-dependent or time-independent schemes.

physics.chem-ph↗

arXiv2026

Quantum Dynamical and isotopic effects for Hydrogen isotopes scattering at W(110) surface

We investigate the scattering of hydrogen isotopes at the W(110) surface using both classical and quantum dynamics approaches to elucidate the role of quantum effects in this system. To characterize the scattering process we focus on key observables, including the absorption probability and diffraction channels that we evaluate at the quasi-classical and quantum levels. The quantum dynamics reveal pronounced resonance structures in the absorption curve that we rationalize in terms of diffraction-mediated selective adsorption and focused sticking mechanisms. Diffraction probabilities for reflected trajectories exhibit strong quantum effects at low incident energies, where classical dynamics underestimate the back scattering probability. These effects become less pronounced with increasing isotope mass, from hydrogen to tritium, however discrepancies between the classical and quantum description persist at low incident energies.

physics.chem-ph↗

arXiv2025

Roadmap for Molecular Benchmarks in Nonadiabatic Dynamics

Simulating the coupled electronic and nuclear response of a molecule to light excitation requires the application of nonadiabatic molecular dynamics. However, when faced with a specific photophysical or photochemical problem, selecting the most suitable theoretical approach from the wide array of available techniques is not a trivial task. The challenge is further complicated by the lack of systematic method comparisons and rigorous testing on realistic molecular systems. This absence of comprehensive molecular benchmarks remains a major obstacle to advances within the field of nonadiabatic molecular dynamics. A CECAM workshop, Standardizing Nonadiabatic Dynamics: Towards Common Benchmarks, was held in May 2024 to address this issue. This Perspective highlights the key challenges identified during the workshop in defining molecular benchmarks for nonadiabatic dynamics. Specifically, this work outlines some preliminary observations on essential components needed for simulations and proposes a roadmap aiming to establish, as an ultimate goal, a community-driven, standardized molecular benchmark set.

physics.chem-ph↗

arXiv2023

Charge transfer of polyatomic molecules in ion-atom hybrid traps: Stereodynamics in the millikelvin regime

Rate constants for the charge transfer reaction between N${}_{2}$H${}^{+}$ and Rb in the mK regime are measured in an ion-atom hybrid trap and are found to be lower than the Langevin capture limit. Multireference ab initio computation of the potential energy surfaces involved in the reaction reveals that the low-temperature charge transfer is hindered by short-range features highly dependent on the collision angle and is promoted by a deformation of the molecular frame. The present study highlights the importance of polyatomic effects and of stereodynamics in cold molecular ion-neutral collisions.

physics.atom-ph↗

arXiv2021

AutoMeKin2021: An open-source program for automated reaction discovery

AutoMeKin2021 is an updated version of tsscds2018, a program for the automated discovery of reaction mechanisms (J. Comput. Chem. 2018, 39, 1922-1930). This release features a number of new capabilities: rare-event molecular dynamics simulations to enhance reaction discovery, extension of the original search algorithm to study van der Waals complexes, use of chemical knowledge, a new search algorithm based on bond-order time series analysis, statistics of the chemical reaction networks, a web application to submit jobs, and other features. The source code, manual, installation instructions and the website link are available at: https://rxnkin.usc.es/index.php/AutoMeKin

physics.chem-ph↗

arXiv2020

Infrared spectra of neutral polycyclic aromatic hydrocarbons by machine learning

The Interest in polycyclic aromatic hydrocarbons (PAHs) spans numerous fields and infrared spectroscopy is usually the method of choice to disentangle their molecular structure. In order to compute vibrational frequencies, numerous theoretical studies employ either quantum calculation methods, or empirical potentials, but it remains difficult to combine the accuracy of the first approach with the computational cost of the second. In this work, we employed Machine Learning techniques to develop a potential energy surface and a dipole mapping based on an artificial neural network (ANN) architecture. Altogether, while trained on only 11 small PAH molecules, the obtained ANNs are able to retrieve the infrared spectra of those small molecules, but more importantly of 8 large PAHs different from the training set, thus demonstrating the transferability of our approach.

physics.chem-ph↗

arXiv2018

Accuracy of Potfit-based potential representations and its impact on the performance of (ML-)MCTDH

Quantum molecular dynamics simulations with MCTDH or ML-MCTDH perform best if the potential energy surface (PES) has a sum-of-products (SOP) or multi-layer operator (MLOp) structure. Here we investigate four different POTFIT-based methods for representing a general PES as such a structure, among them the novel random-sampling multi-layer Potfit (RS-MLPF). We study how the format and accuracy of the PES representation influences the runtime of a benchmark (ML-)MCTDH calculation, namely the computation of the ground state of the ${\text{H}_3\text{O}_2}^-$ ion. Our results show that compared to the SOP format, the MLOp format leads to a much more favorable scaling of the (ML-)MCTDH runtime with the PES accuracy. At reasonably high PES accuracy, ML-MCTDH calculations thus become up to 20 times faster, and taken to the extreme, the RS-MLPF method yields extremely accurate PES representations (global root-mean-square error of $\sim 0.1\,\text{cm}^{-1}$) which still lead to only moderate computational demands for ML-MCTDH.

physics.chem-ph↗

arXiv2018

Entangled Photonic-Nuclear Molecular Dynamics of LiF in Quantum Optical Cavities

The quantum photodynamics of a simple diatomic molecule with a permanent dipole immersed within an optical cavity containing a quantized radiation field is studied in detail. The chosen molecule under study, lithium fluoride (LiF), is characterized by the presence of an avoided crossing between the two lowest $^1Σ$ potential energy curves (covalent-ionic diabatic crossing). Without field, after prompt excitation from the ground state $1\; ^1Σ$, the excited nuclear wave packet moves back and forth in the upper $2\; ^1Σ$ state, but in the proximity of the avoided crossing, the non-adiabatic coupling transfers part of the nuclear wave packet to the lower $1\; ^1Σ$ state, which eventually leads to dissociation. The quantized field of a cavity also induces an additional light crossing in the modified dressed potential energy curves with similar transfer properties. To understand the entangled photonic-nuclear dynamics we solve the time dependent Schrödinger equation by using the multiconfigurational time dependent Hartree method (MCTDH). The single mode quantized field of the cavity is represented in the coordinate space instead of in the Fock space, which allows us to deal with the field as an additional vibrational mode within the MCTDH procedure on equal footing. We prepare the cavity with different quantum states of light, namely, Fock states, coherent states and squeezed coherent states. Our results reveal pure quantum light effects on the molecular photodynamics and the dissociation yields of LiF, which are quite different from the light-undressed case and that cannot be described in general by a semiclassical approach using classical electromagnetic fields.

physics.chem-ph↗