Abstract
The new ONIOM (our own n-layered integrated molecular orbital and molecular mechanics) approach has been proposed and shown to be successful in reproducing benchmark calculations and experimental results. ONIOM3, a three-layered version, divides a system into an active part treated at a very high level of ab initio molecular orbital theory like CCSD(T), a semiactive part that includes important electronic contributions and is treated at the HF or MP2 level, and a nonactive part that is handled using force field approaches. The three-layered scheme allows us to study a larger system more accurately than the previously proposed two-layered schemes IMOMO, which can treat a medium size system very accurately, and IMOMM, which can handle a very large system with modest accuracy. This three-layered scheme has been applied to activation barriers for the Diels−Alder reaction of acrolein + isoprene, acrolein + 2-tert-butyl-1,3-butadiene, and ethylene + 1,4-di-tert-butyl-1,3-butadiene. In general, the results for both geometry optimizations and single point energy calculations agree well with benchmark predictions and experimental results. The scheme has also been applied to the transition state for the oxidative addition of H2 to Pt(P(t-Bu)3)2. The activation energy of this 83-atom reaction is predicted to be 14.2 kcal/mol with the ONIOM3(CCSD(T):MP2:MM3) method.
Keywords
ONIOMChemistryIsopreneAb initioBenchmark (surveying)Energy minimizationMolecular orbitalComputational chemistryAcroleinAtom (system on chip)Physical chemistryMoleculeCatalysisOrganic chemistryCopolymer
Affiliated Institutions
Related Publications
Problematic Energy Differences between Cumulenes and Poly-ynes: Does This Point to a Systematic Improvement of Density Functional Theory?
Relative energetics of the C3H4 (allene (1) and propyne (2)), C5H4 (penta-1,2,3,4-tetraene (3) and penta-1,3-diyne (4)), and C7H4 (hepta-1,2,3,4,5,6-hexaene (5) and hepta-1,3,5-...
Highly Accurate Coupled Cluster Potential Energy Curves for the Benzene Dimer: Sandwich, T-Shaped, and Parallel-Displaced Configurations
State-of-the-art electronic structure theory has been applied to generate potential energy curves for the sandwich, T-shaped, and parallel-displaced configurations of the simple...
Structural destabilization induced by lithium intercalation in MoS<sub>2</sub> and related compounds
2H-MoS 2 is a semiconductor with a hexagonal layered structure. Each Mo atom is prismatically coordinated by six S atoms. Our in situ X-ray diffraction results indicate that, up...
Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction
Abstract A new density functional (DF) of the generalized gradient approximation (GGA) type for general chemistry applications termed B97‐D is proposed. It is based on Becke's p...
Density functional theory augmented with an empirical dispersion term. Interaction energies and geometries of 80 noncovalent complexes compared with <i>ab initio</i> quantum mechanics calculations
Abstract Standard density functional theory (DFT) is augmented with a damped empirical dispersion term. The damping function is optimized on a small, well balanced set of 22 van...
Publication Info
- Year
- 1996
- Type
- article
- Volume
- 100
- Issue
- 50
- Pages
- 19357-19363
- Citations
- 1932
- Access
- Closed
External Links
Social Impact
Altmetric
PlumX Metrics
Social media, news, blog, policy document mentions
Citation Metrics
1932
OpenAlex
Cite This
Mats Svensson,
Stéphane Humbel,
Robert D. J. Froese
et al.
(1996).
ONIOM: A Multilayered Integrated MO + MM Method for Geometry Optimizations and Single Point Energy Predictions. A Test for Diels−Alder Reactions and Pt(P(<i>t</i>-Bu)<sub>3</sub>)<sub>2</sub> + H<sub>2</sub> Oxidative Addition.
The Journal of Physical Chemistry
, 100
(50)
, 19357-19363.
https://doi.org/10.1021/jp962071j
Identifiers
- DOI
- 10.1021/jp962071j