Počet záznamov: 1
Penta- and tetracarbonyls of Ru, Os, and Hs: electronic structure, bonding, and volatility
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$a 10.1063/1.4983125 $2 DOI 100 $a 20170811a2017 m y slo 03 ba 101 0-
$a eng 102 $a US 200 1-
$a Penta- and tetracarbonyls of Ru, Os, and Hs: electronic structure, bonding, and volatility $f V. Pershina, M. Iliaš 330 $a Calculations of the electronic structures and properties of M(CO)(5) and M(CO)(4), where M = Ru, Os, and Hs, have been performed using a variety of relativistic methods such as density functional theory and Dirac-Coulomb correlated ones implemented in program packages such as ADF, DIRAC, and ReSpect. The obtained results show that trends in spectroscopic properties of the M(CO)(5) species in group 8 follow the same pattern as that of other compounds of group 4 through group 8 elements. The calculated first M-CO bond dissociation energy (FBDE) of Hs(CO)(5) turned out to be significantly weaker than that of Os(CO)(5). This was obtained both at the scalar relativistic and spin-orbit levels of theory. The reason for that is the relativistic destabilization and the expansion of the 6d AOs, responsible for weaker sigma-forth and pi-back donations in the Hs compound. Thus, the FBDEs of M(CO)(5) have a Lambda-shape behavior in the row Ru-Os-Hs. The non-relativistic FBDEs steadily increase in this row. Using the results of the molecular calculations and a molecule-slab dispersion interaction model, the volatility of the group-8 carbonyls was estimated as adsorption enthalpies, Delta H-ads, on surfaces of quartz and Teflon used in gas-phase chromatography experiments. It was found that Hs(CO)(5) should be almost as volatile as the homologs; however, its interaction strength with these surfaces should be somewhat larger than that of both Ru(CO)(5) and Os(CO)(5), while the M(CO)(4) (M = Ru, Os, and Hs) molecules should be non-volatile. It will, therefore, be difficult to distinguish between group-8 M(CO)(5) species by measurements of their volatility as Delta H-ads on inert surfaces with error bars of similar to 4 kJ/mol. Published by AIP Publishing. 463 -1
$1 001 umb_un_cat*0293227 $1 011 $a 0021-9606 $1 011 $a 1089-7690 $1 200 1 $a The Journal of Chemical Physics $v Vol. 146, no. 18 (2017), art. no. 184306 $1 210 $a New York $c American Institute of Physics $d 2017 606 0-
$3 umb_un_auth*0207960 $a karbonylové zlúčeniny 606 0-
$3 umb_un_auth*0261554 $a tetrakarbonyly $X tetracarbonyls 606 0-
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$3 umb_un_auth*0235039 $a Pershina $b Valeria $9 50 $4 070 701 -1
$3 umb_un_auth*0173565 $a Iliaš $b Miroslav $p UMBFP08 $4 070 $9 50 $f 1975- $T Katedra chémie 801 -0
$a SK $b BB301 $g AACR2 $9 unimarc sk T85 $x existuji fulltexy
Počet záznamov: 1