Double-substitution-based diagnostics for coupled-cluster and Møller–Plesset perturbation theory

1999 ◽  
Vol 310 (5-6) ◽  
pp. 568-576 ◽  
Author(s):  
Ida M.Beck Nielsen ◽  
Curtis L. Janssen
Keyword(s):  
Perturbation Theory ◽  
Coupled Cluster ◽  
Double Substitution ◽  
Moller Plesset ◽  
Plesset Perturbation Theory

scholarly journals Cis/Trans Energetics in Epoxide, Thiirane, Aziridine and Phosphirane Containing Cyclopentanols: Effects of Intramolecular OH⋯O, S, N and P Contacts

Molecules ◽  
2019 ◽  
Vol 24 (14) ◽  
pp. 2523 ◽  
Author(s):  
Ben E. Smith ◽  
Jeremy M. Carr ◽  
Gregory S. Tschumper
Keyword(s):  
Density Functional Theory ◽  
Perturbation Theory ◽  
Vibrational Frequency ◽  
Density Functional ◽  
Computational Analysis ◽  
Intramolecular Interactions ◽  
Coupled Cluster ◽  
Functional Theory ◽  
Moller Plesset ◽  
Plesset Perturbation Theory

A recent computational analysis of the stabilizing intramolecular OH⋯O contact in 1,2-dialkyl-2,3-epoxycyclopentanol diastereomers has been extended to thiiriane, aziridine and phosphirane analogues. Density functional theory (DFT), second-order Møller-Plesset perturbation theory (MP2) and CCSD(T) coupled-cluster computations with simple methyl and ethyl substituents indicate that electronic energies of the c i s isomers are lowered by roughly 3 to 4 kcal mol−1 when the OH group of these cyclopentanol systems forms an intramolecular contact with the O, S, N or P atom on the adjacent carbon. The results also suggest that S and P can participate in these stabilizing intramolecular interactions as effectively as O and N in constrained molecular environments. The stabilizing intramolecular OH⋯O, OH⋯S, OH⋯N and OH⋯P contacts also increase the covalent OH bond length and significantly decrease the OH stretching vibrational frequency in every system with shifts typically on the order of −41 cm−1.

Sign in / Sign up

Export Citation Format

Share Document