A theoretical study of the linear versus bent geometry for several MX2 molecules: MgF2, CaH2, CaF2, CeO2 and YbCl2

Kock, Roger L. De; Peterson, Michael A.; Timmer, Linda K.; Baerends, Evert Jan; Vernooijs, P.

doi:10.1016/s0277-5387(00)84004-8

Cited by 78 publications

(80 citation statements)

References 96 publications

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“…Additionally, NBO analysis of the CaH 2 monomer reveals that the hybridization of the central Ca atom involves mainly sp (93.51%) by the MP2 method while the hybridization is mainly sd (94.86%) by the B3LYP method. This is in good agreement with previous results giving sp (linear) vs. sd (bent) hybridization for the CaH 2 molecule[15]. As was pointed out above, for the same complex, although the CaH 2 structures calculated by MP2 and B3LYP methods differ from one another, the HH bond distances,  c value at HH BCPs, and charge transfer between fragments are almost identical and consequently result in very similar HH interaction energies being given by the two methods.…”

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confidence: 92%

“…Many investigations of the interactions between CaH 2 and organic or inorganic molecules have been reported, which have included DHB systems with CaH 2 as a proton-accepting molecule [14]. It is worth pointing out that, in different studies, CaH 2 has been suggested to have two alternative geometries, linear or bent [15,16]. An attempt to measure the infrared spectrum of CaH 2 in the gas phase was unsuccessful [17].…”

Section: Introductionmentioning

confidence: 99%

“…An attempt to measure the infrared spectrum of CaH 2 in the gas phase was unsuccessful [17]. In calculations at the Hartree-Fock level [15,18], it was shown that the predicted structure changes from bent to linear, with the equilibrium HCaH angle ranging from 127° to 180°, depending on the size and quality of the one-particle basis set. From size-consistent and high-precision ab initio calculations, Koput [19] predicted the CaH 2 molecule to be slightly bent at equilibrium by the CCSD(T) method with a HCaH angle of 164°, and the barrier to linearity was calculated to be just 6 cm -1 .…”

Section: Introductionmentioning

confidence: 99%

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Does the molecular structure of CaH2 affect the dihydrogen bonding in CaH2 … HY (Y = CH3, C2H3, C2H, CN, and NC) complexes? A quantum chemistry study using MP2 and B3LYP methods

Liu

Bai

et al. 2011

Sci. China Chem.

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Second-order Møller-Plesset (MP2) and density functional theory (DFT) calculations have been carried out in order to investigate the structures and properties of dihydrogen-bonded CaH 2 HY (Y = CH 3 , C 2 H 3 , C 2 H, CN, and NC) complexes. Our calculations revealed two possible structures for CaH 2 in CaH 2 HY complexes: linear (I) and bent (II). The bond lengths, interaction energies, and strengths for HH interactions obtained by both MP2 and B3LYP methods are quite close to each other. It was found that the interaction energy decreases with increasing electron density at the Ca-H bond critical point. Atom-in-molecule (AIM) results show that for all of Ca-HH-Y interactions considered here, the Laplacian of the electron density at the HH bond critical point is positive, indicating the electrostatic nature of these Ca-HH-Y dihydrogen bonded systems. dihydrogen bond, interaction energy, NBO, AIM theory, bond critical point

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supporting

confidence: 92%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Does the molecular structure of CaH2 affect the dihydrogen bonding in CaH2 … HY (Y = CH3, C2H3, C2H, CN, and NC) complexes? A quantum chemistry study using MP2 and B3LYP methods

Liu

Bai

et al. 2011

Sci. China Chem.

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“…Its ground state configuration is bent (for review and discussion see ref. 4). We have found that to describe the bending on the SCF level, it is necessary to include more than one d-function into the basis set.…”

Section: Introductionmentioning

confidence: 99%

6‐31G* basis set for third‐row atoms

et al. 2001

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Medium basis sets based upon contractions of Gaussian primitivesare developed for the third-row elements Ga through Kr. The basis functions generalize the 6-31G and 6-31G * sets commonly used for atoms up to Ar. A reexamination of the 6-31G * basis set for K and Ca developed earlier leads to the inclusion of 3d orbitals into the valence space for these atoms. Now the 6-31G basis for the whole third-row K through Kr has six primitive Gaussians for 1s, 2s, 2p, 3s, and 3p orbitals, and a split-valence pair of three and one primitives for valence orbitals, which are 4s, 4p, and 3d. The nature of the polarization functions for third-row atoms is reexamined as well. The polarization functions for K, Ca, and Ga through Kr are single set of Cartesian d-type primitives. The polarization functions for transition metals are defined to be a single 7f set of uncontracted primitives. Comparison with experimental data shows good agreement with bond lengths and angles for representative vapor-phase metal complexes.

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“…[4][5][6][7][8][9][10][11][12] The dihalides of light alkaline earth elements are all linear, while some of the heavier members of this family are bent with a bond angle in the range from 100 to 155°. The energy difference between bent and linear configurations of these triatomic molecules is known to be rather small, of the order of 0.04-0.12 eV per molecule, 6 presenting a stringent test for any theoretical method. The bent geometry was also observed for a number of Cp 2 M compounds, where Cp refers to the cyclopentadienyl ring C 5 H 5 , the pentamethylcyclopentadienyl ligand C 5 Me 5 , or even more complex cyclopentadienyl-based ligands.…”

Section: Introductionmentioning

confidence: 99%

On the Accuracy of the Total Energy Pseudopotential Scheme Applied to Small Molecules

Milman¹,

Lee

1996

J. Phys. Chem.

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The accuracy of the calculation of the equilibrium geometry of small molecules using the pseudopotential solid state code CASTEP is analyzed. The results of the density functional calculations are presented for alkaline earth dihalides and for the metal-organic molecule Ba(C 5 H 5 ) 2 . The density functional theory predicts qualitatively correct geometry in all cases where the accuracy of 0.01 eV in total energy is sufficient to distinguish between different local extrema. CASTEP implementation of the gradient-corrected exchangecorrelation functional is shown to be in all cases superior to the local density approximation approach.

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A theoretical study of the linear versus bent geometry for several MX2 molecules: MgF2, CaH2, CaF2, CeO2 and YbCl2

Cited by 78 publications

References 96 publications

Does the molecular structure of CaH2 affect the dihydrogen bonding in CaH2 … HY (Y = CH3, C2H3, C2H, CN, and NC) complexes? A quantum chemistry study using MP2 and B3LYP methods

Does the molecular structure of CaH2 affect the dihydrogen bonding in CaH2 … HY (Y = CH3, C2H3, C2H, CN, and NC) complexes? A quantum chemistry study using MP2 and B3LYP methods

6‐31G* basis set for third‐row atoms

On the Accuracy of the Total Energy Pseudopotential Scheme Applied to Small Molecules

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