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A novel treatment of non-adiabatic couplings is proposed. The derivation starts from the long-known, but not well-known, fact that the wave function of the complete system of elctrons and nuclei can be written, without approximation, as a…

材料科学 · 物理学 2007-05-23 Nikitas I. Gidopoulos , E. K. U. Gross

An extension is given for the standard two component model of adiabatic, Born-Oppenheimer (BO) electronic states in a polyatonic molecule, by use of Mathieu functions of arbitrary order. The curl or compatibility conditions for the…

化学物理 · 物理学 2016-09-08 R. Englman , A. Yahalom , M. Baer

We present a novel nonadiabatic perturbation theory (NAPT) for correlated systems of electrons and nuclei beyond the Born-Oppenheimer (BO) approximation. The essence of the method is to exploit the smallness of the electronic-to-nuclear…

化学物理 · 物理学 2025-11-05 Matisse Wei-Yuan Tu , E. K. U. Gross

This report presents a new approach for treating the coupling of electrons and nuclei in quantum mechanical calculations for molecules and condensed matter. It includes the standard "Born-Oppenheimer approximation" as a special case but…

化学物理 · 物理学 2013-06-28 Gerald I. Kerley

The (stationary) Schr\"{o}dinger equation for atomistic systems is solved using the adiabatic potential energy curves (PECs) and the associated adiabatic approximation. Despite being very simplistic, this approach is very powerful and used…

化学物理 · 物理学 2023-12-22 Ryan P. Brady , Charlie Drury , Sergei N. Yurchenko , Jonathan Tennyson

We analyze the entanglement between electronic and nuclear motions in molecular wave functions, by using different widely used ansatzes in molecular Hamiltonian models (H$^+_2$ in 1D and the Shin-Metiu model); namely, i) Born-Oppenheimer…

量子物理 · 物理学 2025-11-13 Juan F. P. Mosquera , Jose Luis Sanz-Vicario

The role of electron-nuclear entanglement on the validity of the Born-Oppenheimer (BO) approximation is investigated. While nonadiabatic couplings generally lead to entanglement and to a failure of the BO approximation, surprisingly the…

量子物理 · 物理学 2016-05-24 Artur F. Izmaylov , Ignacio Franco

Ultralong-range Rydberg molecules (ULRM) are highly imbalanced bound systems formed via the low-energy scattering of a Rydberg electron with a ground-state atom. We investigate for $^{23}$Na the $d$-state and the energetically close-by…

原子物理 · 物理学 2023-07-26 Rohan Srikumar , Frederic Hummel , Peter Schmelcher

Vibrational energies and wave functions of the triplet state of the H3+ ion have been determined. In the calculations, the ground and first excited triplet electronic states are included as well as the non-Born-Oppenheimer coupling between…

化学物理 · 物理学 2016-05-25 Alexander Alijah , Viatcheslav Kokoouline

An asymptotic approach for a Schroedinger type equation with non selfadjoint Hamiltonian of a special type in the case of two close degeneracy (turning) points is developed. Both real and complex degeneracy points are treated by a method of…

数学物理 · 物理学 2021-07-20 Ignat Fialkovsky , Maria Perel

We study effects of nonadiabatic couplings in a model of a diatomic molecule in the context of attosecond transient absorption spectroscopy. By using a model system consisting of four diabatic electronic states and with a variable strength…

原子物理 · 物理学 2021-03-03 Nikolaj S. W. Ravn , Lars Bojer Madsen

We investigate the quantum mechanics of a single particle constrained to move along an arbitrary smooth reference curve by a confinement that is allowed to vary along the waveguide. The Schr\"odinger equation is evaluated in the adapted…

量子物理 · 物理学 2014-03-26 J. Stockhofe , P. Schmelcher

The nitrate radical NO$_3$ plays an important role in atmospheric chemistry, yet many aspects of its coupled and anharmonic vibronic structure remain elusive. Here, using an accurate, coupled full-dimensional diabatic potential that…

化学物理 · 物理学 2024-09-26 Henrik R. Larsson , Alexandra Viel

We investigate the non-adiabatic quantum dynamics of ultralong-range Rydberg molecules using a vibronically coupled two-channel treatment. The two channels are composed of coupled trilobite and butterfly electronic states, formed as a…

原子物理 · 物理学 2026-03-17 Felix Giering , Rohan Srikumar , Peter Schmelcher

The adiabatic Born-Oppenheimer approximation is considered to be a robust approach that very rarely breaks down. Consequently, it is predominantly utilized to address various electron-phonon properties in condensed matter physics. By…

超导电性 · 物理学 2023-03-01 Nina Girotto , Dino Novko

A system of two bilinearly coupled harmonic oscillators has been solved analytically by using the Born-Oppenheimer (BO) product wavefunction ansatz and the phase-space bound trajectory approach [J. S. Molano et al., Chem. Phys. Lett.…

量子物理 · 物理学 2021-08-27 Carlos A. Arango

The interaction between electronic and vibrational degrees of freedom is an important mechanism in nonequilibrium charge transport through molecular nanojunctions. While adiabatic polaron-type coupling has been studied in great detail, new…

介观与纳米尺度物理 · 物理学 2022-06-10 Christoph Kaspar , André Erpenbeck , Jakob Bätge , Christian Schinabeck , Michael Thoss

By going beyond the Born-Oppenheimer approximation and treating the non-adiabatic coupling terms (NACTs) as equivalent to a frictional force in a molecular system, the classical equations of motion are solved for a test case of H3+. Using…

This work identifies geometric effects on dynamics due to nonadiabatic couplings in Born Oppenheimer systems and provides a systematic method for deriving corrections to mixed quantum-classical methods. Specifically, an exact path integral…

化学物理 · 物理学 2007-05-23 Vinod Krishna

We investigate polyatomic ultralong-range Rydberg molecules consisting of three ground state atoms bound to a Rydberg atom via $s$- and $p$-wave interactions. By employing the finite basis set representation of the unperturbed Rydberg…

原子物理 · 物理学 2016-08-03 Christian Fey , Markus Kurz , Peter Schmelcher
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