Atomization Energies of LnX Molecules (Ln = Sm, Eu, and Yb; X = Cl, Br, and I)

Sergeev, Dmitry; Моталов, В. Б.; Бутман, М. Ф.; Kiselev, Artem E.; Кудин, Л. С.; Krämer, Karl

doi:10.1021/je500550s

Cited by 8 publications

(6 citation statements)

References 26 publications

(69 reference statements)

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“…In a few instances, the composite values of D 0 ° seem to be superior to their experimental counterparts. In particular, this observation holds for D 0 ° (YbI) experimentally derived by Sergeev et al: 62.3 ± 4.6 kcal·mol –1 (ref ) and 67.6 ± 2.4 kcal·mol –1 (ref ). The latter value is in conspicuous error, whereas the other one hardly overlaps with the composite result of 58.2 kcal·mol –1 .…”

Section: Resultssupporting

confidence: 63%

Toward Chemical Accuracy in ab Initio Thermochemistry and Spectroscopy of Lanthanide Compounds: Assessing Core–Valence Correlation, Second-Order Spin–Orbit Coupling, and Higher Order Effects in Lanthanide Diatomics

Solomonik

Смирнов

2017

J. Chem. Theory Comput.

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The higher order (HO) correlation beyond the coupled-cluster single double (triple) CCSD(T) level of theory, second-order spin-orbit coupling (SOC), and core-valence (CV) correlation effects on bond length, r, vibrational frequency, ω, and dissociation energy, D, are studied for a set of 17 lanthanide containing diatomics, including lanthanum, europium, ytterbium, and lutetium oxides and halides. Convergence in the magnitudes of the SOC, CV, and HO corrections with respect to basis set size is examined using a sequence of double, triple, and quadruple-ζ basis sets, with the complete basis set (CBS) limit estimates provided in most cases. The CV effects on D, r, and ω are calculated to amount up to 1.3 kcal·mol, 0.008 Å, and 5 cm, respectively. A detailed analysis of the origin of the CV effect with a particular accounting for various subvalence shells reveals that, generally, the Ln 4d correlation makes a major contribution, although in some instances the lower-lying 4sp shells contribute largely and even more substantially than 4d. The second-order SOC effect evaluated via two-component and four-component relativistic techniques proves to be non-negligible, especially for heavier species, e.g., LaI, in which it is as large as 0.8 kcal·mol in D, 0.002 Å in r, and 1.3 cm in ω. Higher order correlation effects assessed through the CCSDT(Q) level are mostly less than 0.8 kcal·mol, 0.004 Å, and 5 cm; however, in species with prominence of nondynamical correlation, e.g., EuO, YbF, and LuO, the HO correction can amount to 1.2-1.6 kcal·mol, 0.005-0.008 Å, and 8-30 cm in D, r, and ω, respectively. In general, the [CCSD(T)+CV]/CBS + SOC + HO composite results are in good agreement with the available experimental data, exhibiting a mean absolute deviation of 1.8 kcal·mol in D, 0.0023 Å in r, and 3.5 cm in ω. A significant experimental outlier, the bond length in YbI, is revealed, implying the need for re-examination of the experimental data.

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Section: Resultssupporting

confidence: 63%

Toward Chemical Accuracy in ab Initio Thermochemistry and Spectroscopy of Lanthanide Compounds: Assessing Core–Valence Correlation, Second-Order Spin–Orbit Coupling, and Higher Order Effects in Lanthanide Diatomics

Solomonik

Смирнов

2017

J. Chem. Theory Comput.

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“…Solomonik and Smirnov studied YbF and YbCl using the CCSD(T) approach. Their computed r e and ω e values, extrapolated to the basis set limit, were in excellent agreement with the experiment − as was the D 0 value for YbCl. Note, however, there is no definitive experimental D 0 value for YbF for comparison.…”

Section: Introductionsupporting

confidence: 60%

Thermochemistry of Gaseous Ytterbium and Gadolinium Hydroxides and Oxyhydroxides

Bauschlicher

Jacobson

2021

J. Phys. Chem. A

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Gd2O3 and Yb2O3 are the proposed constituents of advanced coating systems in combustion environments. In such environments, they are exposed to high-temperature water vapor, which would lead to gaseous hydroxide formation. Thermodynamic parameters are reported for YbO n (OH) m and GdO n (OH) m species. We first study the MH, MO, MF, and MCl (M = Yb and Gd) species, where some experimental data exist. Structures and spectroscopic constants were calculated at the B3LYP level. For YbO n (OH) m , the B3LYP approach is used in conjunction with an effective core potential, while for GdO n (OH) m , it was necessary to use all-electron basis sets. Enthalpies of formation were calculated with a BD(T) approach. The enthalpies of formation, entropies, and heat capacities were added to a thermochemical database. Hydroxide and oxyhydroxide vapor pressures are calculated above pure Yb2O3, Gd2O3, and Y2O3 in 50% H2O/Ar from 1000 to 3000 K. Hydroxide and oxyhydroxide vapor pressures are also calculated for potential coating compositions.

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“…These constants are in better accordance with the experimental values than those calculated by the UCCSD(T) method for the 174 Yb 79 Br isotopologue . In terms of the dissociation energy D e , our calculated value is 295.2 kJ/mol and those calculated at the UCCSD(T) level of theory are 505.8 and 451.7 kJ/mol (ref ), whereas the experimental value is 316 kJ/mol (ref ). From above, it is noticed that our MRCI calculation significantly improves the theoretical D e value.…”

Section: Results and Discussionsupporting

confidence: 85%

“… a Present work using the CASSCF/MRCI method, ECP28MWB_segmented for Yb, and the ECP10MDF_AV5Z basis set for Br. b Reference : UCCSD(T) method, ECP28MDF basis set for Yb. c Reference : UCCSD(T) method, WTBS basis set for Yb. d Reference : exp. e Reference : experimental study for Yb(174)Br(79). f Reference : experimental study for Yb(174)Br(81). g Reference : exp. h Reference : exp. i Reference : exp. …”

Section: Results and Discussionmentioning

confidence: 99%

Electronic Structure Calculations with the Spin Orbit Effect of the Low-Lying Electronic States of the YbBr Molecule

et al. 2019

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This work presents an electronic structure study employing multireference configuration interaction MRCI calculations with Davidson correction (+Q) of the ytterbium monobromide YbBr molecule. Adiabatic potential energy curves (PECs), dipole moment curves, and spectroscopic constants (such as Re, ωe, Be, De, Te, and μe) of the low-lying bound electronic states are determined. The ionic character of the YbBr molecule at the equilibrium position is also discussed. With spin–orbit effects, 30 low-lying states in Ω = 1/2, 3/2, 5/2, 7/2 representation are probed. The electronic transition dipole moment is calculated between the investigated states and then used to determine transition coefficients, for example, the Einstein coefficient of spontaneous emission Aij and emission oscillator strength fij. Vibrational parameters such as Eν, Bν, Dν, Rmin, and Rmax of the low vibrational levels of different bound states in both Λ and Ω representations are also calculated. Upon calculating the Franck–Condon factors, they are found to be perfectly diagonal between three couples of low-lying excited states. Vibrational Einstein coefficients and radiative lifetimes are computed as well for the lowest vibrational transitions. Most of the data reported in this work are presented here for the first time in the literature. Very good accordance is obtained in comparison with the previously reported constants by means of experimental methods.

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Atomization Energies of LnX Molecules (Ln = Sm, Eu, and Yb; X = Cl, Br, and I)

Cited by 8 publications

References 26 publications

Toward Chemical Accuracy in ab Initio Thermochemistry and Spectroscopy of Lanthanide Compounds: Assessing Core–Valence Correlation, Second-Order Spin–Orbit Coupling, and Higher Order Effects in Lanthanide Diatomics

Toward Chemical Accuracy in ab Initio Thermochemistry and Spectroscopy of Lanthanide Compounds: Assessing Core–Valence Correlation, Second-Order Spin–Orbit Coupling, and Higher Order Effects in Lanthanide Diatomics

Thermochemistry of Gaseous Ytterbium and Gadolinium Hydroxides and Oxyhydroxides

Electronic Structure Calculations with the Spin Orbit Effect of the Low-Lying Electronic States of the YbBr Molecule

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