arXiv subjects

Marjan Mirahmadi

Publications and source records attributed to Marjan Mirahmadi.

12 recordsLinked to original sources

arXiv2026

Direct three body dynamics govern ion atom recombination and barrierless termolecular reactions

For over a century, termolecular, or third order, chemical reactions have been explained by the Lindemann Hinshelwood mechanism, assuming sequential stabilization via bimolecular encounters. Here, we demonstrate that barrierless termolecular reactions are fundamentally governed by direct three body dynamics. Using classical trajectory calculations in hyperspherical coordinates, we quantitatively reproduce ion atom recombination kinetics across a wide temperature range without invoking intermediate complexes or steady state assumptions. Our results not only resolve longstanding discrepancies between theory and experiment, but also establish a general mechanistic framework for barrierless termolecular reactions, with implications spanning atmospheric chemistry, plasma physics, and ultracold chemistry.

physics.atom-ph↗

arXiv2023

Three-body recombination in physical chemistry

Three-body recombination, or ternary association, is a termolecular reaction in which three particles collide, forming a bound state between two, whereas the third escapes freely. Three-body recombination reactions play a significant role in many systems relevant to physics and chemistry. In particular, they are relevant in cold and ultracold chemistry, quantum gases, astrochemistry, atmospheric physics, physical chemistry, and plasma physics. As a result, three-body recombination has been the subject of extensive work during the last 50 years, although primarily from an experimental perspective. Indeed, a general theory for three-body recombination remains elusive despite the available experimental information. Our group recently developed a direct approach based on classical trajectory calculations in hyperspherical coordinates for three-body recombination to amend this situation, leading to a first principle explanation of ion-atom-atom and atom-atom-atom three-body recombination processes. This review aims to summarize our findings on three-body recombination reactions and identify the remaining challenges in the field.

physics.chem-ph↗

arXiv2022

Ion-atom-atom three-body recombination: from the cold to the thermal regime

We present a study on ion-atom-atom reaction A+A+B$^+$ in a wide range of systems and collision energies ranging from 100$~μ$K to 10$^5~$K, analyzing the two possible products: molecules and molecular ions. The dynamics is performed via a direct three-body formalism based on a classical trajectory method in hyperspherical coordinates developed in [J. Chem. Phys. $\textbf{140}$, 044307 (2014)]. Our chief finding is that the dissociation energy of the molecular ion product acts as a threshold energy separating the low and high energy regimes. In the low energy regime, the long-range tail of the three-body potential dictates the fate of the reaction and the main reaction product. On the contrary, in the high energy regime, the short-range of atom-atom and atom-ion interaction potential dominates the dynamics, enhancing molecular formation for the low energy regime.

physics.atom-ph↗

arXiv2022

Mapping atomic trapping in an optical superlattice onto the libration of a planar rotor in electric fields

We show that two seemingly unrelated problems - the trapping of an atom in an optical superlattice (OSL) and the libration of a planar rigid rotor in combined electric and optical fields - have isomorphic Hamiltonians. Formed by the interference of optical lattices whose spatial periods differ by a factor of two, OSL gives rise to a periodic potential that acts on atomic translation via the AC Stark effect. The latter system, also known as the generalized planar pendulum (GPP), is realized by subjecting a planar rigid rotor to combined orienting and aligning interactions due to the coupling of the rotor's permanent and induced electric dipole moments with the combined fields. The mapping makes it possible to establish correspondence between concepts developed for the two eigenproblems individually, such as localization on the one hand and orientation/alignment on the other. Moreover, since the GPP problem is conditionally quasi-exactly solvable (C-QES), so is atomic trapping in an OSL. We make use of both the correspondence and the quasi-exact solvability to treat ultracold atoms in an optical superlattice as a semifinite-gap system. The band structure of this system follows from the eigenenergies and their genuine and avoided crossings obtained previously for the GPP as analytic solutions of the Whittaker-Hill equation. These solutions characterize both the squeezing and the tunneling of atoms trapped in an optical superlattice and pave the way to unraveling their dynamics in analytic form.

cond-mat.quant-gas↗

arXiv2022

Hyperradial distribution function of few-body problems: a new arena for extreme value theory

This work explores classical capture models for few-body systems via a Monte Carlo method in hyperspherical coordinates. In particular, we focus on van der Waals and charged-induced dipole interactions. As a result, we notice that, independently of the number of particles and interparticle interaction, the capture hyperradial distribution function follows a Fréchet distribution, a special type of the generalized extreme value distribution. Besides, we elaborate on the fundamentals of such universal feature using the general extreme value theory, thus, establishing a connection between extreme value theory and few-body physics.

physics.chem-ph↗

arXiv2022

Ion-atom-atom three-body recombination in cold hydrogen and deuterium plasmas

We present a detailed study about ion-atom-atom three-body recombination in hydrogen and deuterium plasmas based on classical trajectory calculations in hyperspherical coordinates. Our results, due to the predominant role of the long-range charged-induced dipole interaction, indicate that H$_2^+$ and D$_2^+$ are the main reaction products in the case of hydrogen and deuterium plasmas, respectively. Besides, we find a more steep energy-dependent reaction rate when the collision energy surpasses the dissociation energy of the molecular ion, thus entering a new dynamical regime dominated by short-range interactions.

physics.atom-ph↗

arXiv2021

Ozone formation in ternary collisions: Theory and experiment reconciled

Absorbing UV radiation, ozone protects life on Earth and plays a fundamental role in Earth's temperature balance. The formation of ozone occurs through the ternary recombination reaction: O$_2$+O+M $\rightarrow$ O$_3$+M, where M can be N$_2$, O$_2$ or Ar. Here, we developed a theoretical approach capable of modeling the formation of ozone molecules in ternary collisions, and applied it to the reaction with M=Ar because of extensive experimental data available. The rate coefficients for the direct formation of O$_3$ in ternary collisions O+O$_2$+Ar were computed for the first time as a function of collision energy, and thermally-averaged coefficients were derived for temperatures 5-900~K leading to a good agreement with available experimental data for temperatures 100-900~K. The present study shows that the formation of ozone in ternary collisions O+O$_2$+Ar at temperatures below 200~K proceeds through a formation of a temporary complex ArO$_2$, while at temperatures above 1000~K, the reaction proceeds mainly through a formation of long-lived vibrational resonances of O$_3^*$. At intermediate temperatures 200~K-1000~K, the process cannot be viewed as a two-step mechanism. In addition, it is found that the majority of O$_3$ molecules formed initially are weakly bound.

physics.chem-ph↗

arXiv2021

Classical threshold law for the formation of van der Waals molecules

We study the role of pairwise long-range interactions in the formation of van der Waals molecules through direct three-body recombination processes A + B + B $\rightarrow$ AB + B, based on a classical trajectory method in hyperspherical coordinates developed in our earlier works [J. Chem. Phys. 140, 044307 (2014); J. Chem. Phys. 154, 034305 (2021)]. In particular, we find the effective long-range potential in hyperspherical coordinates with an exact expression in terms of dispersion coefficients of pairwise potentials. Exploiting this relation, we derive a classical threshold law for the total cross section and the three-body recombination rate yielding an analytical expression for the three-body recombination rate as a function of the pairwise long-range coefficients of the involved partners.

physics.chem-ph↗

arXiv2021

Quantum dynamics of a planar rotor driven by suddenly switched combined aligning and orienting interactions

We investigate, both analytically and numerically, the quantum dynamics of a planar (2D) rigid rotor subject to suddenly switched-on or switched-off concurrent orienting and aligning interactions. We find that the time-evolution of the post-switch populations as well as of the expectation values of orientation and alignment reflects the spectral properties and the eigensurface topology of the planar pendulum eigenproblem established in our earlier work [Frontiers in Physics 2, 37 (2014); Eur. Phys. J. D 71, 149 (2017)]. This finding opens the possibility to examine the topological properties of the eigensurfaces experimentally as well as provides the means to make use of these properties for controlling the rotor dynamics in the laboratory.

quant-ph↗

arXiv2021

On the formation of van der Waals complexes through three-body recombination

In this work, we show that van der Waals molecules X-RG (where RG is the rare gas atom) may be created through direct three-body recombination collisions, i.e., X + RG + RG $\rightarrow$ X-RG + RG. In particular, the three-body recombination rate at temperatures relevant for buffer gas cell experiments is calculated via a classical trajectory method in hyperspherical coordinates [J. Chem. Phys. 140, 044307 (2014)]. As a result, it is found that the formation of van der Waals molecules in buffer gas cells (1 K $\lesssim T \lesssim 10$ K) is dominated by the long-range tail (distances larger than the LeRoy radius) of the X-RG interaction. For higher temperatures, the short-range region of the potential becomes more significant. Moreover, we notice that the rate of formation of van der Walls molecules is of the same order of magnitude independently of the chemical properties of X. As a consequence, almost any X-RG molecule may be created and observed in a buffer gas cell under proper conditions.

physics.chem-ph↗

arXiv2018

Dynamics of polar polarizable rotors acted upon by unipolar electromagnetic pulses: From the sudden to the adiabatic regime

We study, analytically as well as numerically, the dynamics that arises from the interaction of a polar polarizable rigid rotor with single unipolar electromagnetic pulses of varying length, $Δτ$, with respect to the rotational period of the rotor, $τ_r$. In the sudden, non-adiabatic limit, $Δτ\ll τ_r$, we derive analytic expressions for the rotor's wavefunctions, kinetic energies, and field-free evolution of orientation and alignment. We verify the analytic results by solving the corresponding time-dependent Schrödinger equation numerically and extend the temporal range of the interactions considered all the way to the adiabatic limit, $Δτ\gg τ_r$, where general analytic solutions beyond the field-free case are no longer available. The effects of the orienting and aligning interactions as well as of their combination on the post-pulse populations of the rotational states are visualized as functions of the orienting and aligning kick strengths in terms of populations quilts. Quantum carpets that encapsulate the evolution of the rotational wavepackets provide the space-time portraits of the resulting dynamics. The population quilts and quantum carpets reveal that purely orienting, purely aligning, or even-break combined interactions each exhibit a sui generis dynamics. In the intermediate temporal regime, we find that the wavepackets as functions of the orienting and aligning kick strengths show resonances that correspond to diminished kinetic energies at particular values of the pulse duration.

quant-ph↗

arXiv2017

Conditional quasi-exact solvability of the quantum planar pendulum and of its anti-isospectral hyperbolic counterpart

We have subjected the planar pendulum eigenproblem to a symmetry analysis with the goal of explaining the relationship between its conditional quasi-exact solvability (C-QES) and the topology of its eigenenergy surfaces, established in our earlier work [Frontiers in Physical Chemistry and Chemical Physics 2, 1-16, (2014)]. The present analysis revealed that this relationship can be traced to the structure of the tridiagonal matrices representing the symmetry-adapted pendular Hamiltonian, as well as enabled us to identify many more -- forty in total to be exact -- analytic solutions. Furthermore, an analogous analysis of the hyperbolic counterpart of the planar pendulum, the Razavy problem, which was shown to be also C-QES [American Journal of Physics 48, 285 (1980)], confirmed that it is anti-isospectral with the pendular eigenproblem. Of key importance for both eigenproblems proved to be the topological index $κ$, as it determines the loci of the intersections (genuine and avoided) of the eigenenergy surfaces spanned by the dimensionless interaction parameters $η$ and $ζ$. It also encapsulates the conditions under which analytic solutions to the two eigenproblems obtain and provides the number of analytic solutions. At a given $κ$, the anti-isospectrality occurs for single states only (i.e., not for doublets), like C-QES holds solely for integer values of $κ$, and only occurs for the lowest eigenvalues of the pendular and Razavy Hamiltonians, with the order of the eigenvalues reversed for the latter. For all other states, the pendular and Razavy spectra become in fact qualitatively different, as higher pendular states appear as doublets whereas all higher Razavy states are singlets.

quant-ph↗