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A dihedral angle is the angle between two intersecting planes. In chemistry, it is the angle between planes through two sets of three atoms, having two atoms in common. In solid geometry, it is defined as the union of a line and two half-planes that have this line as a common edge. In higher dimensions, a dihedral angle represents the angle between two hyperplanes. The planes of a flying machine are said to be at positive dihedral angle when both starboard and port main planes are upwardly inclined to the lateral axis. When downwardly inclined they are said to be at a negative dihedral angle.

Mathematical background

When the two intersecting planes are described in terms of Cartesian coordinates by the two equations : a_1 x + b_1 y + c_1 z + d_1 = 0 :a_2 x + b_2 y + c_2 z + d_2 = 0 the dihedral angle, \varphi between them is given by: :\cos \varphi = \frac and satisfies 0\le \varphi \le \pi/2. Alternatively, if and are normal vector to the planes, one has :\cos \varphi = \frac where is the dot product of the vectors and is the product of their lengths. The absolute value is required in above formulas, as the planes are not changed when changing all coefficient signs in one equation, or replacing one normal vector by its opposite. However the absolute values can be and should be avoided when considering the dihedral angle of two half planes whose boundaries are the same line. In this case, the half planes can be described by a point of their intersection, and three vectors , and such that , and belong respectively to the intersection line, the first half plane, and the second half plane. The ''dihedral angle of these two half planes'' is defined by : \cos\varphi = \frac, and satisfies 0\le\varphi <\pi.

In polymer physics

In some scientific areas such as polymer physics, one may consider a chain of points and links between consecutive points. If the points are sequentially numbered and located at positions , , , etc. bond vectors are defined by =-, =-, and =-, more generally. This is the case for kinematic chains or amino acids in a protein structure. In these cases, one is often interested in the planes defined by three consecutive points, and the dihedral angle between two consecutive such planes. If an orientation has been chosen for the whole chain, each pair of consecutive points defines a vector, and the sum of all these vectors is the vector pointining from the beginning to the end of the chain. If , and are three consecutive such vectors, one has a situation that is similar to the preceding case, except that the intersection of the planes is oriented. This allows defining a dihedral angle that belongs to the interval . This dihedral angle is defined by :\begin \cos \varphi&=\frac\\ \sin \varphi&=\frac, \end or, using the function atan2, :\varphi=\operatorname(\mathbf_2 \cdot((\mathbf_1 \times \mathbf_2) \times (\mathbf_2 \times \mathbf_3)), |\mathbf_2|\,(\mathbf_1 \times \mathbf_2) \cdot (\mathbf_2 \times \mathbf_3)). This dihedral angle does not depend on the orientation of the chain (order in which the point are considered). In fact, changing this ordering consists of replacing each vector by its opposite vector, and exchanging the indices 1 and 3. Both operations do not change the cosine, and change the sign of the sine. Thus, together, they do not change the angle. A simpler formula for the same dihedral angle is the following (the proof is given below) :\begin \cos \varphi&=\frac\\ \sin \varphi&=\frac, \end or equivalently, :\varphi=\operatorname( |\mathbf_2|\,\mathbf_1 \cdot(\mathbf_2 \times \mathbf_3) , (\mathbf_1 \times \mathbf_2) \cdot (\mathbf_2 \times \mathbf_3)). This can be deduced from previous formulas by using the vector quadruple product formula, and the fact that a scalar triple product is zero if it contains twice the same vector: : (\mathbf_1\times\mathbf_2)\times(\mathbf_2\times\mathbf_3) = \mathbf_2\times\mathbf_3)\cdot\mathbf_1mathbf_2 - \mathbf_2\times\mathbf_3)\cdot\mathbf_2mathbf_1 = \mathbf_2\times\mathbf_3)\cdot\mathbf_1mathbf_2 Special cases are \varphi = \pi, \varphi = +\pi/3 and \varphi = -\pi/3, which are called the ''trans'', ''gauche+'', and ''gauche'' conformations.

In stereochemistry

In stereochemistry, a torsion angle is defined as a particular example of a dihedral angle, describing the geometric relation of two parts of a molecule joined by a chemical bond. Every set of three not-colinear atoms of a molecule defines a plane. When two such planes intersect (i.e., a set of four consecutively-bonded atoms), the angle between them is a dihedral angle. Dihedral angles are used to specify the molecular conformation. Stereochemical arrangements corresponding to angles between 0° and ±90° are called ''syn'' (s), those corresponding to angles between ±90° and 180° ''anti'' (a). Similarly, arrangements corresponding to angles between 30° and 150° or between −30° and −150° are called ''clinal'' (c) and those between 0° and ±30° or ±150° and 180° are called ''periplanar'' (p). The two types of terms can be combined so as to define four ranges of angle; 0° to ±30° synperiplanar (sp); 30° to 90° and −30° to −90° synclinal (sc); 90° to 150° and −90° to −150° anticlinal (ac); ±150° to 180° antiperiplanar (ap). The synperiplanar conformation is also known as the ''syn''- or ''cis''-conformation; antiperiplanar as ''anti'' or ''trans''; and synclinal as ''gauche'' or ''skew''. For example, with ''n''-butane two planes can be specified in terms of the two central carbon atoms and either of the methyl carbon atoms. The ''syn''-conformation shown above, with a dihedral angle of 60° is less stable than the ''anti''-conformation with a dihedral angle of 180°. For macromolecular usage the symbols T, C, G+, G, A+ and A are recommended (ap, sp, +sc, −sc, +ac and −ac respectively).

Proteins

thumb|175px|Depiction of a protein, showing backbone dihedral angles A Ramachandran plot (also known as a Ramachandran diagram or a 'φ'',''ψ''plot), originally developed in 1963 by G. N. Ramachandran, C. Ramakrishnan, and V. Sasisekharan, is a way to visualize energetically allowed regions for backbone dihedral angles ''ψ'' against ''φ'' of amino acid residues in protein structure. The figure at right illustrates the definition of the ''φ'' and ''ψ'' backbone dihedral angles (called ''φ'' and ''φ′'' by Ramachandran). In a protein chain three dihedral angles are defined as ''φ'' (phi), ''ψ'' (psi) and ''ω'' (omega), as shown in the diagram. The planarity of the peptide bond usually restricts ''ω'' to be 180° (the typical ''trans'' case) or 0° (the rare ''cis'' case). The distance between the Cα atoms in the ''trans'' and ''cis'' isomers is approximately 3.8 and 2.9 Å, respectively. The vast majority of the peptide bonds in proteins are ''trans'', though the peptide bond to the nitrogen of proline has an increased prevalence of ''cis'' compared to other amino-acid pairs. The side chain dihedral angles are designated with ''χn'' (chi-''n''). They tend to cluster near 180°, 60°, and −60°, which are called the ''trans'', ''gauche+'', and ''gauche'' conformations. The stability of certain sidechain dihedral angles is affected by the values ''φ'' and ''ψ''. For instance, there are direct steric interactions between the C''γ'' of the side chain in the ''gauche+'' rotamer and the backbone nitrogen of the next residue when ''ψ'' is near -60°.

Converting from dihedral angles to Cartesian coordinates in chains

It is common to represent polymers backbones, notably proteins, in internal coordinates; that is, a list of consecutive dihedral angles and bond lengths. However, some types of computational chemistry instead use cartesian coordinates. In computational structure optimization, some programs need to flip back and forth between these representations during their iterations. This task can dominate the calculation time. For processes with many iterations or with long chains, it can also introduce cumulative numerical inaccuracy. While all conversion algorithms produce mathematically identical results, they differ in speed and numerical accuracy.

Geometry

Every polyhedron has a dihedral angle at every edge describing the relationship of the two faces that share that edge. This dihedral angle, also called the ''face angle'', is measured as the internal angle with respect to the polyhedron. An angle of 0° means the face normal vectors are antiparallel and the faces overlap each other, which implies that it is part of a degenerate polyhedron. An angle of 180° means the faces are parallel, as in a tiling. An angle greater than 180° exists on concave portions of a polyhedron. Every dihedral angle in an edge-transitive polyhedron has the same value. This includes the 5 Platonic solids, the 13 Catalan solids, the 4 Kepler–Poinsot polyhedra, the two quasiregular solids, and two quasiregular dual solids. Given 3 faces of a polyhedron which meet at a common vertex P and have edges AP, BP and CP, the cosine of the dihedral angle between the faces containing APC and BPC is: :\cos\varphi = \frac

See also

*Atropisomer


References


{{Reflist

External links


The Dihedral Angle in Woodworking at Tips.FM


gives a step-by-step derivation of these exact values. Category:Stereochemistry Category:Protein structure Category:Euclidean solid geometry Category:Angle