Beryllium Dimer: A Bond Based on Non-Dynamical Correlation

Khatib, Muammar El; Bendazzoli, Gian Luigi; Evangelisti, Stefano; Helal, Wissam; Leininger, Thierry; Tenti, Lorenzo; Angeli, Celestino

doi:10.1021/jp503145u

Cited by 54 publications

(46 citation statements)

References 37 publications

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“…1is a pronounced hump in the inner-shell post-CCSD(T) corrections curve. We believe that this feature is related to the change in the character of the chemical bond as argued in Ref [18]…”

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confidence: 66%

“…These conclusions have been confirmed by several other authors. [11][12][13][14][15][16][17][18] The fact that the beryllium dimer is an apparently simple yet challenging system has made it a frequent subject of state-of-the-art computational studies. At present the consensus is that the binding energy of the beryllium dimer is in the range 920−940 cm −1 and the bond length is approximately 2.44 Å.…”

Section: Introductionmentioning

confidence: 99%

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Ab initio Potential Energy Curve for the Ground State of Beryllium Dimer

Lesiuk

Przybytek

Balcerzak

et al. 2019

J. Chem. Theory Comput.

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This work concerns ab initio calculations of the complete potential energy curve and spectroscopic constants for the ground state X 1 Σ + g of the beryllium dimer, Be 2 .High accuracy and reliability of the results is one of the primary goals of the paper. To this end we apply large basis sets of Slater-type orbitals combined with highlevel electronic structure methods including triple and quadruple excitations. The effects of the relativity are also fully accounted for in the theoretical description. For the first time the leading-order quantum electrodynamics effects are fully incorporated for a many-electron molecule. Influence of the finite nuclear mass corrections (post-Born-Oppenheimer effects) turns out to be completely negligible for this system. The predicted well-depth (D e = 934.5 ± 2.5 cm −1 ) and the dissociation energy (D 0 = 808.0 cm −1 ) are in a very good agreement with the most recent experimental data. We confirm the existence of the weakly bound twelfth vibrational level [Patkowski et al., Science 326, 1382(2009] and predict that it lies just about 0.5 cm −1 below the onset of the continuum.

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“…1is a pronounced hump in the inner-shell post-CCSD(T) corrections curve. We believe that this feature is related to the change in the character of the chemical bond as argued in Ref [18]…”

mentioning

confidence: 66%

Section: Introductionmentioning

confidence: 99%

Ab initio Potential Energy Curve for the Ground State of Beryllium Dimer

Lesiuk

Przybytek

Balcerzak

et al. 2019

J. Chem. Theory Comput.

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“…By applying the multireference configuration interaction (MRCI) method, Liu et al found the interaction energy to be as large as 810 cm −1 and confirmed the existence of the minimum around 2.5Å. These findings were later verified by several independent MRCI studies [23][24][25][26][27][28][29][30]. Therefore, it is now well established that Be 2 is not a van der Waals molecule.…”

Section: Introductionmentioning

confidence: 91%

Reexamination of the calculation of two-center, two-electron integrals over Slater-type orbitals. III. Case study of the beryllium dimer

et al. 2015

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In this paper we present results of ab-initio calculations for the beryllium dimer with basis set of Slater-type orbitals (STOs). Nonrelativistic interaction energy of the system is determined using the frozen-core full configuration interaction calculations combined with high-level coupled cluster correction for inner-shell effects. Newly developed STOs basis sets, ranging in quality from double to sextuple zeta, are used in these computations. Principles of their construction are discussed and several atomic benchmarks are presented. Relativistic effects of order α 2 are calculated perturbatively by using the Breit-Pauli Hamiltonian and are found to be significant. We also estimate the leading-order QED effects. Influence of the adiabatic correction is found to be negligible. Finally, the interaction energy of the beryllium dimer is determined to be 929.0 ± 1.9 cm −1 , in a very good agreement with the recent experimental value. The results presented here appear to be the most accurate ab-initio calculations for the beryllium dimer available in the literature up to date and probably also one of the most accurate calculations for molecular systems containing more than four electrons.

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“…The computed PEC by the restricted Hartree-Fock (RHF) method is purely repulsive and could not predict a stable molecule [21]. It seems that the formation of this molecule is the result of the very small part of the total energy which is called the correlation energy (E corr ).…”

Section: Introductionmentioning

confidence: 99%

“…2s and 2p orbitals in the current study) and determinant expansion could calculate most part of this type of the correlation. The Complete Active Space Self-consistent Field (CASSCF) method (in the following the method is denoted as CAS(n,m) for the sake of simplicity which indicates a calculation incorporating an active space explicitly correlating n electrons in m orbitals) is a popular method in this case and has been used widely in studying the beryllium species [21][22][23]. However, the recently published paper [21] show that the accuracy of CAS computations are extremely dependent on the employed active space and basis set (cc-pV6Z was used in the latter paper); although larger active space could not give necessarily more accurate results [21].…”

Section: Introductionmentioning

confidence: 99%