Search NASA⌕ Search
Home/Archive/DOE OSTI

DOE OSTI · 21408608

Generating optimal Sturmian basis functions for atomic problems

Randazzo, J M·Frapiccini, A L·Colavecchia, F D·Ancarani, L U·Gasaneo, G
View original source ↗Export metadata ↓

Abstract

In this paper we discuss the optimization of Sturmian basis functions by studying bound atomic systems within the configuration interaction method. Our investigation clearly shows how the fulfillment of correct physical boundary conditions at short and large distances from the nucleus improves the convergence rate of the method. This is illustrated first through a one-electron atom, and then with the two-electron systems. For the ground state of the helium atom, and with 35 Sturmian functions per electron and angular momenta, we obtain an energy of -2.903 712 820 a.u., outperforming previous similar calculations [Bromley and Mitroy, Int. J. Quantum Chem. 107, 1150 (2007)].

Explore related subjects

74 ATOMIC AND MOLECULAR PHYSICSANGULAR MOMENTUMATOMSBOUNDARY CONDITIONSCONFIGURATION INTERACTIONCONVERGENCEELECTRONSELEMENTARY PARTICLESELEMENTSENERGY LEVELSFERMIONSFLUIDSFUNCTIONSGASESGROUND STATESHELIUMLEPTONSNONMETALSNUCLEIOPTIMIZATIONRARE GASES

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Randazzo, J M, Frapiccini, A L, Colavecchia, F D, Ancarani, L U, Gasaneo, G. 2010-04-15. Generating optimal Sturmian basis functions for atomic problems. https://doi.org/10.1103/physreva.81.042520

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related reports

DOE OSTI2026

Geometric decoherence time in Lindbladian dynamics

The onset of decoherence in open many-body systems lacks a dynamical timescale grounded in the loss of bipartite entanglement. Here, we introduce the geometric decoherence time, defined as the earliest moment the monotone relation between logarithmic negativity and Rényi-$\frac{1}{2}$ entropy—exactly equal across any bipartition for pure states—breaks down under open-system evolution, signaling entropy growth without accompanying entanglement growth. We establish this criterion in both single-particle Gaussian dynamics and many-body Lindbladian evolution. We show that quantum mutual information provides a complementary long-time diagnostic: Its asymptotic vanishing is equivalent to factorization of the steady state across the bipartition, a condition strictly stronger than separability, and whenever a product steady state is approached exponentially in trace norm, negativity and mutual information share the same decay rate. In the presence of a strong symmetry, this tracking can fail—residual classical correlations can survive after entanglement has vanished. In the Kitaev chain with balanced gain and loss, we derive a closed-form solution and show that the topological phase sustains longer coherence times than the trivial phase at identical dissipation, with a local minimum at the chiral-symmetric point. In the interacting XXZ chain, exact many-body evolution shows that local 𝑍 dephasing preserves residual classical correlations, whereas gain and loss restore the mutual-information tracking of negativity. Furthermore, our results establish the geometric decoherence time as a dynamical scale tracking the onset of decoherence.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Restricted Partition Function Semiclassical Transition State Theory (RPF-SCTST): Applications to Reactions Involving Hydrogen Cyanide, Hydrogen Peroxide, and Formaldehyde Oxide

We demonstrate the efficiency of the numerical calculation of thermal semiclassical transition state theory (SCTST) rates across several representative chemical reactions using the restricted partition function (RPF)─viz a function that depends only on the imaginary action associated with a reaction. Here, we treat the potential energy surfaces (PESs) through fourth order expansions around the saddle point and integrate the Hamiltonian up to second order in employing vibrational perturbation theory. We apply this formalism to uni- and bimolecular reactions with different─though relatively high─barrier heights to uncover the influence of the barrier properties, minimal energies, and separability of the rotational motion on rate constants and tunneling corrections. Although all modes are coupled within the RPF, we found in our numerical examples that the rotational component in the absence of significant rotational distortions can be separated from the vibrational contributions. Moreover, a classical treatment of the rotational contribution is adequate over the temperature range from approximately 100 to 1000 K. We also found that the choice of DFT basis set can lead to variations in rate constants of up to an order of magnitude. Lastly, different schemes for counting eligible energy levels result in rate constants that differ by no more than a factor of 2, with the remaining discrepancies attributed to the treatment of near-convergent levels in perturbation theory.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Seniority eigenstate configuration interaction

Zero-seniority methods have shown great promise for the description of strongly correlated electronic systems. Other seniority sectors have been much less explored, and in particular, the maximal seniority sector and zero seniority have the same underlying algebraic structure. We introduce a seniority eigenstate configuration interaction in which the wave function is constrained to have good fixed local seniority for each paired orbital, by which we mean we partition orbitals into a pairing set with seniority zero, and a spin set with seniority one. Here, we show how to build the effective Hamiltonian for this ansatz, and demonstrate that high-seniority wave functions have unexpectedly excellent accuracy for strongly correlated fermionic systems, with accuracy competitive with or better than seniority zero for the Hubbard model and for the dissociation of the nitrogen molecule.

74 ATOMIC AND MOLECULAR PHYSICS↗