Theoretical study of the LiNa molecule beyond the Born–Oppenheimer approximation: adiabatic and diabatic potential energy curves, radial coupling, adiabatic correction, dipole moments and vibrational levels

Mabrouk, N.; Zrafi, Wissem; Berriche, H.

doi:10.1080/00268976.2019.1605098

Cited by 10 publications

(6 citation statements)

References 65 publications

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“…In conjunction with eqs 4−6 and the results by Baer, 37 Mabrouk and Berriche, 83 and Smith, 84 a simple and powerful expression for the matrix element of the diagonal DDR term K for the coupled two-electronic state problem is obtained…”

Section: Description Of the Diabatization Of A Two-electronic-state S...mentioning

confidence: 95%

Numerical Equivalence of Diabatic and Adiabatic Representations in Diatomic Molecules

Brady,

Drury,

Yurchenko

et al. 2024

J. Chem. Theory Comput.

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The (time-independent) Schrodinger equation for atomistic systems is solved by using the adiabatic potential energy curves (PECs) and the associated adiabatic approximation. In cases where interactions between electronic states become important, the associated nonadiabatic effects are taken into account via derivative couplings (DDRs), also known as nonadiabatic couplings (NACs). For diatomic molecules, the corresponding PECs in the adiabatic representation are characterized by avoided crossings. The alternative to the adiabatic approach is the diabatic representation obtained via a unitary transformation of the adiabatic states by minimizing the DDRs. For diatomics, the diabatic representation has zero DDR and nondiagonal diabatic couplings ensue. The two representations are fully equivalent and so should be the rovibronic energies and wave functions, which result from the solution of the corresponding Schrodinger equations. We demonstrate (for the first time) the numerical equivalence between the adiabatic and diabatic rovibronic calculations of diatomic molecules using the ab initio curves of yttrium oxide (YO) and carbon monohydride (CH) as examples of two-state systems, where YO is characterized by a strong NAC, while CH has a strong diabatic coupling. Rovibronic energies and wave functions are computed using a new diabatic module implemented in the variational rovibronic code DUO. We show that it is important to include both the diagonal Born−Oppenheimer correction and nondiagonal DDRs. We also show that the convergence of the vibronic energy calculations can strongly depend on the representation of nuclear motion used and that no one representation is best in all cases.

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Section: Description Of the Diabatization Of A Two-electronic-state S...mentioning

confidence: 95%

Numerical Equivalence of Diabatic and Adiabatic Representations in Diatomic Molecules

Brady,

Drury,

Yurchenko

et al. 2024

J. Chem. Theory Comput.

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“…The current work builds upon our previous theoretical investigations − ,,− concerning the structural and spectroscopic properties of neutral and charged diatomic molecules composed of alkali and alkaline earth atoms. In this article, we extend our calculations to study the electronic properties and elastic collisions of the charged diatomic systems FrLi + and FrNa + using the same method.…”

Section: Introductionmentioning

confidence: 98%

Accurate Ab Initio Investigation of Electronic and Radiative Properties, and Cross Sections for Charged Diatomic Systems FrLi⁺ and FrNa⁺

Ghanmi,

Berriche

2023

ACS Omega

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This paper presents an extensive ab initio investigation of the electronic properties and elastic collisions of charged diatomic systems FrLi + and FrNa + . We employ an accurate ab initio approach using nonempirical pseudopotentials for Li + , Na + , and Fr + cores. We calculate the potential energy curves of the ground state and low-lying excited states of 2 Σ + , 2 Π, and 2 Δ symmetries, identifying and interpreting avoided crossings between higher 2 Σ + and 2 Π states. The spectroscopic parameters, transition dipole moments, and vibrational energies associated with 1−3 2 Σ + states are calculated, along with the radiative lifetimes of the vibrational states trapped in the 2 2 Σ + state. Using accurate potential energy data, we evaluate partial and total cross sections across a wide range of energies. At low energies (<1 mK), the elastic cross section follows the Wigner law threshold comportment, while at high energies, it scales as E −1/3 . To the best of our knowledge, no theoretical or experimental data have been collected on these charged diatomic systems until now. Hence, we proceeded to analyze our findings by comparing them with data acquired from comparable systems. The information pertaining to electronic structures, spectroscopic parameters, transition properties, and collision data provided in this work is expected to serve as a valuable guideline for future theoretical and experimental research on each considered system.

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“…µ d π ≈ δ s [63]. In the context of traditional molecular physics, CIs play an important role in molecular dynamics as they can cause fast non-radiative transitions between electronic states [64][65][66][67], Jahn-Teller distortions [68,69], and surface hoppings [70,71] to name a few examples. The study of non-adiabatic effects in the vicinity of conical intersections has been proven to be necessary for understanding a wide-range of natural phenomena such as photo stability of DNA [72,73], photoisomerization [74,75] and reaction mechanisms involving photosynthesis [76].…”

Section: Introductionmentioning

confidence: 99%

Non-adiabatic interaction effects in the spectra of ultralong-range Rydberg molecules

Rohan¹,

Hummel²,

Schmelcher³

2023

Preprint

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Theoretical study of the LiNa molecule beyond the Born–Oppenheimer approximation: adiabatic and diabatic potential energy curves, radial coupling, adiabatic correction, dipole moments and vibrational levels

Cited by 10 publications

References 65 publications

Numerical Equivalence of Diabatic and Adiabatic Representations in Diatomic Molecules

Numerical Equivalence of Diabatic and Adiabatic Representations in Diatomic Molecules

Accurate Ab Initio Investigation of Electronic and Radiative Properties, and Cross Sections for Charged Diatomic Systems FrLi⁺ and FrNa⁺

Non-adiabatic interaction effects in the spectra of ultralong-range Rydberg molecules

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Theoretical study of the LiNa molecule beyond the Born–Oppenheimer approximation: adiabatic and diabatic potential energy curves, radial coupling, adiabatic correction, dipole moments and vibrational levels

Cited by 10 publications

References 65 publications

Numerical Equivalence of Diabatic and Adiabatic Representations in Diatomic Molecules

Numerical Equivalence of Diabatic and Adiabatic Representations in Diatomic Molecules

Accurate Ab Initio Investigation of Electronic and Radiative Properties, and Cross Sections for Charged Diatomic Systems FrLi+ and FrNa+

Non-adiabatic interaction effects in the spectra of ultralong-range Rydberg molecules

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Product

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Accurate Ab Initio Investigation of Electronic and Radiative Properties, and Cross Sections for Charged Diatomic Systems FrLi⁺ and FrNa⁺