Ab initio based double-sheeted DMBE potential energy surface for N3(2A″) and exploratory dynamics calculations
1Departamento de Quimica, Universidade de Coimbra, Coimbra, Portugal.
The Journal of Physical Chemistry. A
|September 21, 2011
Summary
We developed an accurate potential energy surface for nitrogen atom (N(3)) reactions. This computational tool aids in studying nitrogen allotropes and azides dynamics.
Area of Science:
- Chemical Physics
- Computational Chemistry
- Quantum Chemistry
Background:
- Accurate potential energy surfaces (PESs) are crucial for understanding chemical reactions.
- Nitrogen allotropes and azides are important in materials science and energetic compounds.
- The N(3) radical's electronic states are key to these systems.
Purpose of the Study:
- To construct a global, accurate, double-sheeted potential energy surface (PES) for the lowest doublet states of the N(3) radical.
- To ensure the PES accurately describes symmetry properties and dissociation limits.
- To provide a reliable computational tool for dynamics studies.
Main Methods:
- Utilized the double many-body expansion (DMBE) method for PES construction.
- Calibrated the PES using multireference configuration interaction (MRCI) energies.
- Employed a quasiclassical trajectory (QCT) study for N((2)D) + N(2) collisions.
Main Results:
- Developed a globally accurate double-sheeted PES for N(3) lowest doublet states.
- The PES correctly reproduces stationary structures and dissociation limits.
- QCT study demonstrated the PES's utility in dynamics simulations.
Conclusions:
- The developed PES is suitable for both classical and quantum dynamics studies.
- This PES serves as a foundational component for larger nitrogen systems.
- The work advances computational modeling of nitrogen-containing compounds.
Related Concept Videos
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...
02:06Newman Projections
Different notations are used to represent the three-dimensional structure of molecules on two-dimensional surfaces. One of the most commonly used representations is the dash-wedge formula. The dashed wedges, solid wedges, and the plane lines indicate the groups situated behind the plane, coming out of the plane, and in the plane, respectively.
The organic molecules rotate across the single bonds leading to numerous temporary three-dimensional structures of varying energy known as conformers.
The organic molecules rotate across the single bonds leading to numerous temporary three-dimensional structures of varying energy known as conformers.
01:13Force and Potential Energy in One Dimension
Force can be calculated from the expression for potential energy, which is a function of position. The component of a conservative force, in a particular direction, equals the negative of the derivative of the corresponding potential energy with respect to the displacement in that direction. For regions where potential energy changes rapidly with displacement, the work done and force is maximum. Also, when force is applied along the positive coordinate axis, the potential energy decreases with...
03:24Hybridization of Atomic Orbitals I
The mathematical expression known as the wave function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes. This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the linear combination of atomic orbitals. The new orbitals that...
02:36Molecular Geometry and Dipole Moments
The VSEPR theory can be used to determine the electron pair geometries and molecular structures as follows:
02:38Valence Bond Theory and Hybridized Orbitals
According to valence bond theory, a covalent bond results when: (1) an orbital on one atom overlaps an orbital on a second atom, and (2) the single electrons in each orbital combine to form an electron pair. The strength of a covalent bond depends on the extent of overlap of the orbitals involved. Maximum overlap is possible when the orbitals overlap on a direct line between the two nuclei.
A σ bond (single bond in a Lewis structure) is a covalent bond in which the electron density is...
A σ bond (single bond in a Lewis structure) is a covalent bond in which the electron density is...