Estimate of the total energy of the beryllium hydride molecule

Lao, R.C.; Riter, J. R.

doi:10.1021/j100867a059

Cited by 9 publications

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“…Covalent Molecule . In agreement with previous theoretical studies, − BeH 2 is calculated to have a linear, centrosymmetric structure. However, the present best estimate for D 0 (34.8 kcal/mol) is somewhat lower than most previous theoretical estimates. ,,, The discrepancy can be attributed to the higher correlation used in the present study because the MP2 D e (−40.7 kcal/mol) agrees with previous similar calculations.…”

Section: Discussionsupporting

confidence: 90%

“…In agreement with previous theoretical studies, [27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42] BeH 2 is calculated to have a linear, centrosymmetric structure. However, the present best estimate for D 0 (34.8 kcal/ mol) is somewhat lower than most previous theoretical estimates.…”

Section: Discussionsupporting

confidence: 89%

“…Motivated by structural, thermochemical, and polymerization questions and attracted by the low number of valence electrons, many theoretical investigations of BeH 2 (refs −42) and (BeH 2 ) x (refs −36, 38, 42) have been reported. The calculations indicate that BeH 2 is a linear, symmetric molecule with a BeH bond length of about 1.33 Å and dissociation energy of about 35−40 kcal/mol with respect to Be + H 2 .…”

Section: Introductionmentioning

confidence: 99%

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σ Bond Activation by Cooperative Interaction with ns² Atoms: Be + nH₂, n = 1−3

Sharp

Gellene

2000

J. Phys. Chem. A

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Ab initio investigations at the MP2, CCSD(T), and MRCISD levels of theory with augmented triple-basis sets have identified and characterized various stationary points on the Be/(H 2 ) n , n ) 1-3, hypersurfaces. The van der Waals complexes, Be(H 2 ) n , are very weakly bound (D e ) 0.08-0.32 kcal/mol with respect to H 2 loss) with H 2 /H 2 interactions playing an important role in determining equilibrium structures which can be understood in terms of the various relevant long-range potentials. The covalent molecule, BeH 2 , is found to have a linear, centrosymmetric structure and to be strongly bound with respect to Be + H 2 , in agreement with previous calculations. BeH 2 interacts weakly with additional H 2 molecules (D e < 0.75 kcal/mol) which are positioned parallel to the near-linear BeH 2 moiety in the equilibrium structures of the BeH 2 (H 2 ) n-1 complexes. Of particular interest is the dramatic change in the nature of the transition state for BeH 2 production depending on the number of H 2 molecules present. For n ) 1, the reaction proceeds stepwise: first breaking the H 2 bond and forming one BeH bond followed by forming the second BeH bond. This process has an activation energy of about 56 kcal/mol. For n ) 2, the reaction proceeds via a pericyclic mechanism through a planar cyclic transition state where two H 2 bonds are broken while simultaneously two BeH bonds and one new H 2 bond are formed. The activation energy for this process decreases from the n ) 1 value to about 38 kcal/mol. For n ) 3, the reaction proceeds through a true insertion mechanism with the addition of the third H 2 molecule, decreasing the activation energy to about 33 kcal/mol. The results are discussed in comparison to the isoelectronic B + /nH 2 systems where significant σ bond activation through a cooperative interaction mechanism has been identified.

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