| SYS | | 0248994 |
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| LBL | | ---naa--22--------450- |
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| 005 | | 20240509140630.6 |
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| 014 | | $a 000401368900019 $2 CCC |
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| 014 | | $a 000401368900019 $2 WOS CC. SCIE |
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| 014 | | $a 2-s2.0-85018879488 $2 SCOPUS |
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| 017 | 70 | $a 10.1063/1.4983125 $2 DOI |
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| 100 | | $a 20170811a2017 m y slo 03 ba |
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| 101 | 0- | $a eng |
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| 102 | | $a US |
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| 200 | 1- | $a Penta- and tetracarbonyls of Ru, Os, and Hs: electronic structure, bonding, and volatility $f V. Pershina, M. Iliaš |
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| 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. |
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| 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 |
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| 606 | 0- | $3 umb_un_auth*0207960 $a karbonylové zlúčeniny |
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| 606 | 0- | $3 umb_un_auth*0261554 $a tetrakarbonyly $X tetracarbonyls |
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| 606 | 0- | $3 umb_un_auth*0261555 $a pentakarbonyly $X pentacarbonyls |
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| 615 | | $n 544 $a Fyzikálna chémia |
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| 675 | | $a 544 |
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| 700 | -1 | $3 umb_un_auth*0235039 $a Pershina $b Valeria $9 50 $4 070 |
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| 701 | -1 | $3 umb_un_auth*0173565 $a Iliaš $b Miroslav $p UMBFP08 $4 070 $9 50 $f 1975- $T Katedra chémie |
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| 801 | -0 | $a SK $b BB301 $g AACR2 $9 unimarc sk |
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| T85 | | $x existuji fulltexy |
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