Semiempirical Relativistic Molecular Structure Calculations

Pyykkö, Pekka

doi:10.1007/978-1-4613-0711-2_4

Cited by 6 publications

(1 citation statement)

References 148 publications

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“…For relativistic effect in chemistry, Dirac stated that it would be of little use in the consideration of molecular structures or ordinary chemical reactions in 1929, and chemists by and large agreed with his assertion until the 1970s. , Nevertheless, the relativistic effects turn out to be noticeable in all the elements and are significant for the ground states of molecules roughly beginning from the elements in the sixth row (Cs–Rn), especially for lanthanides, actinides, and the superheavy elements of the period table. − For example, the so-called 6s 2 inert pair effect refers to a tendency for this pair of 6s 2 electrons to resist oxidation due to the stabilization resulting from the dominating direct relativistic effects . − Related to relativistic effects, many unexpected and novel properties are brought into the chemistry of the heavier elements with high atomic numbers, − gold and mercury being prominent examples of such. ,− Superheavy elements have especially significant relativistic effects. These elements can be studied by means of the gas-phase chromatography technique due to their strong volatilities, whereby they are deposited on the detector surfaces.…”

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confidence: 99%

Relativity–Induced Bonding Pattern Change in Coinage Metal Dimers M₂ (M = Cu, Ag, Au, Rg)

Wang

et al. 2018

Inorg. Chem.

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The periodic table provides a fundamental protocol for qualitatively classifying and predicting chemical properties based on periodicity. While the periodic law of chemical elements had already been rationalized within the framework of the nonrelativistic description of chemistry with quantum mechanics, this law was later known to be affected significantly by relativity. We here report a systematic theoretical study on the chemical bonding pattern change in the coinage metal dimers (Cu, Ag, Au, Rg) due to the relativistic effect on the superheavy elements. Unlike the lighter congeners basically demonstrating ns- ns bonding character and a 0 ground state, Rg shows unique 6d-6d bonding induced by strong relativity. Because of relativistic spin-orbit (SO) coupling effect in Rg, two nearly degenerate SO states, 0 and 2, exist as candidate of the ground state. This relativity-induced change of bonding mechanism gives rise to various unique alteration of chemical properties compared with the lighter dimers, including higher intrinsic bond energy, force constant, and nuclear shielding. Our work thus provides a rather simple but clear-cut example, where the chemical bonding picture is significantly changed by relativistic effect, demonstrating the modified periodic law in heavy-element chemistry.

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