The periodic table of diatomic molecules—I an algorithm for retrieval and prediction of spectrophysical properties

Hefferlin, Ray; Campbell, R. F.; Gimbel, David; Kuhlman, H.; Cayton, T. E.

doi:10.1016/0022-4073(79)90063-3

Cited by 22 publications

(15 citation statements)

References 18 publications

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“…Consequently, the other areas have gaps, most spectacularly the area with R 1 = R 2 = 1, having H 2 , HeH, HHe, and He 2 on its corners, as can be seen in Fig. (8) of [11]. The second had 15 kinds of areas, as shown in Fig.…”

Section: Fig (2)mentioning

confidence: 97%

“…A graph of D o o of dimers and of oxides of the elements, Fig. (1), demonstrates [11] that zinc, cadmium, and (not shown) mercury molecules, at the ends of the transition-metal series, act like closed-shell rare-gas molecules. This graph led to defining the property surfaces or terrains on coordinate systems specifically suited to two-atom systems, as explained in the next section.…”

Section: A "Eureka!" Moment Late 1976mentioning

confidence: 99%

“…The same was done for Z i of Zn, Cd, and Hg and for Z i of the elements terminating the lanthanoids and actinoids. These lines defined the square and rectangular areas [11] shown in Fig. (2).…”

Section: The Definition Of Fixed-period Areas Of the Diatomic-moleculmentioning

confidence: 99%

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Kronecker-Product Periodic Systems of Small Gas-Phase Molecules and the Search for Order in Atomic Ensembles of Any Phase

Hefferlin¹

2008

CCHTS

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The periodic law, manifested in the chart of the elements, is so fundamental in chemistry and related areas of physics that the question arises "Might periodicity among molecules also be embodied in a periodic system?" This review paper details how a particular periodic system of gas-phase diatomic molecules, allowing for the forecasting of thousands of new data, was developed. It can include ionized and even quarked-nuclei molecules and it coincides with locality (averaging) and the additivity found in some data; it has interesting vector properties, and it may be related in challenging ways to partial order. The review then explains how periodic systems for triatomic and four-atomic species are evolving along a similar path. The systems rest largely upon exhaustive comparisons of tabulated data, relate to some extent to the octet rule, and include reducible representations of the dynamic group SO(4) in higher spaces. Finally, the paper shows how periodicity can be quantified in data for larger molecules. Data for properties of homologous or substituted molecules, in any phase, are quantified with a vector index, and the index for one set can be transformed into that for another set.

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Section: Fig (2)mentioning

confidence: 97%

Section: A "Eureka!" Moment Late 1976mentioning

confidence: 99%

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Kronecker-Product Periodic Systems of Small Gas-Phase Molecules and the Search for Order in Atomic Ensembles of Any Phase

Hefferlin¹

2008

CCHTS

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“…We expect that complete insight into the electronic structure of the minimal catalytic units such as M, MO, MO 2 , and M 2 O 2 enables the building of the maximally efficient catalyst by adding chemical components bottom‐up. The success largely relies on the observation that many chemical properties of small molecules are periodic, leading e. g. to the early concept of a periodic table of diatomics …”

Section: Introductionmentioning

confidence: 99%

“…The success largely relies on the observation that many chemical properties of small molecules are periodic, leading e. g. to the early concept of a periodic table of diatomics. [27][28][29] A major advantage of this strategy is the existence of many more systematic experimental data for small molecular systems than for larger homogeneous and heterogeneous catalytic systems. For the diatomic MO and MO + systems studied in this work, almost all of the 60 bond dissociation enthalpies (BDE) are available for all the 3d, 4d, and 5d systems, enabling full account of the periodicities and trends needed for rational catalyst design.…”

Section: Introductionmentioning

confidence: 99%

Performance of Density Functional Theory for Transition Metal Oxygen Bonds

Moltved

Kepp

2019

ChemPhysChem

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The accuracy of density functional theory (DFT) limits predictions in theoretical catalysis, and strong chemical bonds between transition metals and oxygen pose a particular challenge. We benchmarked 30 diverse density functionals against the bond dissociation enthalpies (BDE) of the 30 MO and 30 MO+ diatomic systems of all the 3d, 4d, and 5d metals, to test universality across the d‐block as required in comparative studies. Seven functionals, B98, B97‐1, B3P86, B2PLYP, TPSSh, B3LYP, and B97‐2, display mean absolute errors (MAE) <30 kJ/mol. In contrast, many commonly used functionals such as PBE and RPBE overestimate M−O bonding by +30 kJ/mol and display MAEs from 48–76 kJ/mol. RPBE and OPBE reduce the over‐binding of PBE but remain very inaccurate. We identify a linear relationship (p‐value 7.6 ⋅ 10−5) between the precision and accuracy of DFT, i. e. inaccurate functionals tend to produce larger, unpredictable random errors. Some functionals commonly deviate from this relationship: Thus, M06‐2X is very precise but not very accurate, whereas B3LYP* and MN15‐L are more accurate but less precise than M06‐2X. The best‐performing hybrids have 10–30 % HF exchange, but this can be relieved by double hybrids (B2PLYP). Most functionals describe trends well, but errors comparing 5d to 4d/3d are ∼10 kJ/mol larger than group‐wise errors, due to uncertainties in the spin‐orbit coupling corrections for effective core potentials, affecting e. g. Pt/Pd or Au/Ag comparisons.

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Periodic table of the elements and the Thomas–Fermi atom

Essén

1982

Int J of Quantum Chemistry

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The periodic table of diatomic molecules—I an algorithm for retrieval and prediction of spectrophysical properties

Cited by 22 publications

References 18 publications

Kronecker-Product Periodic Systems of Small Gas-Phase Molecules and the Search for Order in Atomic Ensembles of Any Phase

Kronecker-Product Periodic Systems of Small Gas-Phase Molecules and the Search for Order in Atomic Ensembles of Any Phase

Performance of Density Functional Theory for Transition Metal Oxygen Bonds

Periodic table of the elements and the Thomas–Fermi atom

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