Related Experiment Video
Updated: Jun 26, 2026
12:11
Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
Published on: April 8, 2020
Interaction of NO molecules with Pd clusters: ab initio density-functional study
Robert Grybos1, Lubomir Benco, Tomas Bucko
1Fakultät für Physik and Center for Computational Material Science, Universität Wien, Sensengasse, A-1090 Wien, Austria.
Journal of Computational Chemistry
|January 6, 2009
Summary
Nitric oxide (NO) strongly adsorbs on small palladium clusters, activating the NO molecule and causing unique geometric and magnetic changes. This study reveals competing energetic effects influencing NO adsorption on palladium nanoclusters.
Area of Science:
- Surface Science
- Computational Chemistry
- Materials Science
Background:
- Nitric oxide (NO) adsorption is crucial for catalysis.
- Understanding NO interaction with metal clusters is key to designing new catalysts.
- Palladium (Pd) clusters exhibit unique properties compared to bulk surfaces.
Purpose of the Study:
- Investigate NO molecule adsorption on small palladium clusters (Pd(n), n=1-6).
- Determine preferred adsorption sites and configurations.
- Analyze the electronic and geometric effects of NO adsorption on Pd clusters.
Main Methods:
- First-principles density-functional theory (DFT) calculations.
- Exploration of vertex, bridge, and hollow adsorption sites.
- Inclusion of anharmonic corrections for vibrational frequency analysis.
Main Results:
- Strong adsorption energies (2-3 eV) observed for NO on Pd clusters.
- NO molecules consistently adsorb in a bent configuration.
- Significant geometric changes and Pd d-orbital rehybridization occur upon adsorption.
- Electron transfer from Pd d-orbitals to NO pi* orbitals activates the NO molecule.
- Palladium clusters exhibit local demagnetization, and the N-O bond lengthens and redshifts.
Conclusions:
- NO adsorption on Pd clusters is energetically favorable and leads to significant structural and electronic modifications.
- The interaction involves a delicate balance between bonding energy and cluster deformation.
- Activated NO on Pd clusters presents opportunities for catalytic applications.
- Computational findings align well with experimental vibrational data, validating the theoretical approach.
Related Concept Videos
02:36Molecular Geometry and Dipole Moments
The VSEPR theory can be used to determine the electron pair geometries and molecular structures as follows:
02:40MO Theory and Covalent Bonding
The molecular orbital theory describes the distribution of electrons in molecules in a manner similar to the distribution of electrons in atomic orbitals. The region of space in which a valence electron in a molecule is likely to be found is called a molecular orbital. Mathematically, the linear combination of atomic orbitals (LCAO) generates molecular orbitals. Combinations of in-phase atomic orbital wave functions result in regions with a high probability of electron density, while...
01:24π Molecular Orbitals of 1,3-Butadiene
Conjugated dienes have lower heats of hydrogenation than cumulated and isolated dienes, making them more stable. The enhanced stabilization of conjugated systems can be understood from their π molecular orbitals.
The simplest conjugated diene is 1,3-butadiene: a four-carbon system where each carbon is sp2-hybridized and has an unhybridized p orbital that contains an unpaired electron. According to molecular orbital theory, atomic orbitals combine to form molecular orbitals such that the number...
The simplest conjugated diene is 1,3-butadiene: a four-carbon system where each carbon is sp2-hybridized and has an unhybridized p orbital that contains an unpaired electron. According to molecular orbital theory, atomic orbitals combine to form molecular orbitals such that the number...
03:51Molecular Orbital Theory II
Molecular Orbital Energy Diagrams
01:24Van der Waals Interactions
Atoms and molecules interact with each other through intermolecular forces. These electrostatic forces arise from attractive or repulsive interactions between particles with permanent, partial, or temporary charges. The intermolecular forces between neutral atoms and molecules are ion–dipole, dipole–dipole, and dispersion forces, collectively known as van der Waals forces.Polar molecules have a partial positive charge on one end and a partial negative charge on the other end of the molecule,...
02:35Molecular Orbital Theory I
Overview of Molecular Orbital Theory