Napredna pretraga

Pregled bibliografske jedinice broj: 204999

Transfer hydrogenation between ethane and ethene: a critical assessment of theoretical procedures


Miller, Daniel J.; Smith, David M.; Chan, Bun C.; Radom, Leo
Transfer hydrogenation between ethane and ethene: a critical assessment of theoretical procedures // Molecular Physics, 104 (2006), 777-794 (međunarodna recenzija, članak, znanstveni)


Naslov
Transfer hydrogenation between ethane and ethene: a critical assessment of theoretical procedures

Autori
Miller, Daniel J. ; Smith, David M. ; Chan, Bun C. ; Radom, Leo

Izvornik
Molecular Physics (0026-8976) 104 (2006); 777-794

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
Transfer hydrogenation; ab initio

Sažetak
The prototypical transfer-hydrogenation reaction between ethane and ethene has been examined with quantum chemistry procedures. Methods used include high-level single-reference procedures such as CCSD(T), BD(T) and CCSDT, high-level multi-reference procedures such as CASPT2, CAS-ACPF and CAS-AQCC, and less computationally demanding density functional theory procedures such as B3-LYP, MPWB1K and BMK. The concerted pathway for this reaction is clearly favoured over the stepwise process. Our best prediction of the concerted barrier is 210 kJ mol– 1. An anti transition structure for the stepwise pathway lies 70 kJ mol– 1 higher in energy. It is found that the concerted transition structure has relatively little biradical character but that incorporation of dynamic correlation is very important for its accurate theoretical description. The stepwise transition structure has considerable biradical character and, among traditional methods, either high-level multi-reference procedures (e.g. CAS-AQCC) or broken-spin-symmetry single-reference procedures (e.g. UBD(T) or UCCSD(T)) are required for reliable results. Broken-spin-symmetry density functional theory methods such as UMPWB1K and UBMK provide a cost-effective alternative for examining both pathways.

Izvorni jezik
Engleski

Znanstvena područja
Kemija



POVEZANOST RADA


Projekt / tema
0098151

Ustanove
Institut "Ruđer Bošković", Zagreb

Autor s matičnim brojem:
David Matthew Smith, (260506)

Časopis indeksira:


  • Current Contents Connect (CCC)
  • Web of Science Core Collection (WoSCC)
    • Science Citation Index Expanded (SCI-EXP)
    • SCI-EXP, SSCI i/ili A&HCI
  • Scopus


Uključenost u ostale bibliografske baze podataka:


  • Chemical Abstracts