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Molecular dipole moment

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Molecular dipole moment

This article is about the electromagnetic phenomenon. For other uses, see dipole (disambiguation).


In physics, there are several kinds of dipole:

  • An electric dipole is a separation of positive and negative charges. The simplest example of this is a pair of electric charges of equal magnitude but opposite sign, separated by some (usually small) distance. A permanent electric dipole is called an electret.
  • A magnetic dipole is a closed circulation of electric current. A simple example of this is a single loop of wire with some constant current flowing through it.[1][2]
  • A current dipole is a flow of current from a sink of current to a source of current within a (usually conducting) medium. Current dipoles are often used to model neuronal sources of electromagnetic fields that can be measured using MEG or EEG technologies.
  • A flow dipole is a separation of a sink and a source. In a highly viscous medium, a two-beater kitchen mixer causes a dipole flow field.
  • An acoustic dipole is the oscillating version of it. A simple example is a dipole speaker.
  • Any scalar or other field may have a dipole moment.

Dipoles can be characterized by their dipole moment, a vector quantity. For the simple electric dipole given above, the electric dipole moment points from the negative charge towards the positive charge, and has a magnitude equal to the strength of each charge times the separation between the charges. (To be precise: for the definition of the dipole moment one should always consider the "dipole limit", where e.g. the distance of the generating charges should converge to 0, while simultaneously the charge strength should diverge to infinity in such a way that the product remains a positive constant.)

For the current loop, the magnetic dipole moment points through the loop (according to the right hand grip rule), with a magnitude equal to the current in the loop times the area of the loop.

In addition to current loops, the electron, among other fundamental particles, has a magnetic dipole moment. This is because it generates a magnetic field that is identical to that generated by a very small current loop. However, to the best of our knowledge, the electron's magnetic moment is not due to a current loop, but is instead an intrinsic property of the electron.[3] It is also possible that the electron has an electric dipole moment, although this has not yet been observed (see electron electric dipole moment for more information).


A permanent magnet, such as a bar magnet, owes its magnetism to the intrinsic magnetic dipole moment of the electron. The two ends of a bar magnet are referred to as poles (not to be confused with monopoles), and are labeled "north" and "south." The dipole moment of the bar magnet points from its magnetic south to its magnetic north pole. The north pole of a bar magnet in a compass points north. However, this means that Earth's geomagnetic north pole is the south pole of its dipole moment, and vice versa.

The only known mechanisms for the creation of magnetic dipoles are by current loops or quantum-mechanical spin since the existence of magnetic monopoles has never been experimentally demonstrated.

The term comes from the Greek δίς (dis), "twice"[4] and πόλος (pòlos), "axis".[5][6]

Classification



A physical dipole consists of two equal and opposite point charges: in the literal sense, two poles. Its field at large distances (i.e., distances large in comparison to the separation of the poles) depends almost entirely on the dipole moment as defined above. A point (electric) dipole is the limit obtained by letting the separation tend to 0 while keeping the dipole moment fixed. The field of a point dipole has a particularly simple form, and the order-1 term in the multipole expansion is precisely the point dipole field.

Although there are no known magnetic monopoles in nature, there are magnetic dipoles in the form of the quantum-mechanical spin associated with particles such as electrons (although the accurate description of such effects falls outside of classical electromagnetism). A theoretical magnetic point dipole has a magnetic field of exactly the same form as the electric field of an electric point dipole. A very small current-carrying loop is approximately a magnetic point dipole; the magnetic dipole moment of such a loop is the product of the current flowing in the loop and the (vector) area of the loop.

Any configuration of charges or currents has a 'dipole moment', which describes the dipole whose field is the best approximation, at large distances, to that of the given configuration. This is simply one term in the multipole expansion when the total charge ("monopole moment") is 0 — as it always is for the magnetic case, since there are no magnetic monopoles. The dipole term is the dominant one at large distances: Its field falls off in proportion to 1/r3, as compared to 1/r4 for the next (quadrupole) term and higher powers of 1/r for higher terms, or 1/r2 for the monopole term.

Molecular dipoles

Many molecules have such dipole moments due to non-uniform distributions of positive and negative charges on the various atoms. Such is the case with polar compounds like hydrogen fluoride (HF), where electron density is shared unequally between atoms. Therefore, a molecule's dipole is an electric dipole with an inherent electric field which should not be confused with a magnetic dipole which generates a magnetic field.

The physical chemist Peter J. W. Debye was the first scientist to study molecular dipoles extensively, and, as a consequence, dipole moments are measured in units named debye in his honor.

For molecules there are three types of dipoles:

  • Permanent dipoles: These occur when two atoms in a molecule have substantially different electronegativity: One atom attracts electrons more than another, becoming more negative, while the other atom becomes more positive. A molecule with a permanent dipole moment is called a polar molecule. See dipole-dipole attractions.
  • Instantaneous dipoles: These occur due to chance when electrons happen to be more concentrated in one place than another in a molecule, creating a temporary dipole. See instantaneous dipole.
  • Induced dipoles: These can occur when one molecule with a permanent dipole repels another molecule's electrons, inducing a dipole moment in that molecule. A molecule is polarized when it carries an induced dipole. See induced-dipole attraction.

More generally, an induced dipole of any polarizable charge distribution ρ (remember that a molecule has a charge distribution) is caused by an electric field external to ρ. This field may, for instance, originate from an ion or polar molecule in the vicinity of ρ or may be macroscopic (e.g., a molecule between the plates of a charged capacitor). The size of the induced dipole is equal to the product of the strength of the external field and the dipole polarizability of ρ.

Dipole moment values can be obtained from measurement of the dielectric constant. Some typical gas phase values in debye units are:[7]


KBr has one of the highest dipole moments because it is a very ionic molecule (which only exists as a molecule in the gas phase).

The overall dipole moment of a molecule may be approximated as a vector sum of bond dipole moments. As a vector sum it depends on the relative orientation of the bonds, so that from the dipole moment information can be deduced about the molecular geometry. 
For example the zero dipole of CO2 implies that the two C=O bond dipole moments cancel so that the molecule must be linear. For H2O the O-H bond moments do not cancel because the molecule is bent. For ozone (O3) which is also a bent molecule, the bond dipole moments are not zero even though the O-O bonds are between similar atoms. This agrees with the Lewis structures for the resonance forms of ozone which show a positive charge on the central oxygen atom.
Resonance Lewis structures of the ozone molecule
An example in organic chemistry of the role of geometry in determining dipole moment is the cis and trans isomers of 1,2-dichloroethene. In the cis isomer the two polar C-Cl bonds are on the same side of the C=C double bond and the molecular dipole moment is 1.90 D. In the trans isomer, the dipole moment is zero because the two C-Cl bond are on opposite sides of the C=C and cancel (and the two bond moments for the much less polar C-H bonds also cancel).

Note that it is critical to verify the geometry of a molecular species before engaging in any calculations of dipole moment. The polarity of individual bonds in a molecule is no guarantee that the molecule is polar. For example, one might readily assume that boron trifluoride is a polar molecule because the difference in electronegativity is greater than the traditionally cited threshold of 1.7. However, due to the equilateral triangular distribution of the fluoride ions about the boron cation center, the molecule as a whole does not exhibit any identifiable pole: one cannot construct a plane that divides the molecule into a net negative part and a net positive part.

Quantum mechanical dipole operator

Consider a collection of N particles with charges qi and position vectors ri. For instance, this collection may be a molecule consisting of electrons, all with chargee, and nuclei with charge eZi, where Zi is the atomic number of the i th nucleus. The physical quantity (observable) dipole has the quantum mechanical dipole operator:

\mathfrak{p} = \sum_{i=1}^N \, q_i \, \mathbf{r}_i \, .

Atomic dipoles

A non-degenerate (S-state) atom can have only a zero permanent dipole. This fact follows quantum mechanically from the inversion symmetry of atoms. All 3 components of the dipole operator are antisymmetric under inversion with respect to the nucleus,

\mathfrak{I} \;\mathfrak{p}\; \mathfrak{I}^{-1} = - \mathfrak{p},

where \stackrel{\mathfrak{p}}{} is the dipole operator and \stackrel{\mathfrak{I}}{}\, is the inversion operator. The permanent dipole moment of an atom in a non-degenerate state (see degenerate energy level) is given as the expectation (average) value of the dipole operator,

\langle \mathfrak{p} \rangle = \langle\, S\, | \mathfrak{p} |\, S \,\rangle, where |\, S\, \rangle is an S-state, non-degenerate, wavefunction, which is symmetric or antisymmetric under inversion: \mathfrak{I}\,|\, S\, \rangle= \pm |\, S\, \rangle. Since the product of the wavefunction (in the ket) and its complex conjugate (in the bra) is always symmetric under inversion and its inverse,

\langle \mathfrak{p} \rangle = \langle\, \mathfrak{I}^{-1}\, S\, | \mathfrak{p} |\, \mathfrak{I}^{-1}\, S \,\rangle

= \langle\,  S\, |  \mathfrak{I}\, \mathfrak{p} \, \mathfrak{I}^{-1}| \, S \,\rangle = -\langle \mathfrak{p} \rangle

it follows that the expectation value changes sign under inversion. We used here the fact that \mathfrak{I}\,, being a symmetry operator, is unitary: \mathfrak{I}^{-1} = \mathfrak{I}^{*}\, and by definition the Hermitian adjoint \mathfrak{I}^*\, may be moved from bra to ket and then becomes \mathfrak{I}^{**} = \mathfrak{I}\,. Since the only quantity that is equal to minus itself is the zero, the expectation value vanishes,

\langle \mathfrak{p}\rangle = 0. In the case of open-shell atoms with degenerate energy levels, one could define a dipole moment by the aid of the first-order Stark effect. This gives a non-vanishing dipole (by definition proportional to a non-vanishing first-order Stark shift) only if some of the wavefunctions belonging to the degenerate energies have opposite parity; i.e., have different behavior under inversion. This is a rare occurrence, but happens for the excited H-atom, where 2s and 2p states are "accidentally" degenerate (see article Laplace–Runge–Lenz vector for the origin of this degeneracy) and have opposite parity (2s is even and 2p is odd).

Field of a static magnetic dipole

In addition to dipoles in electrostatics, it is also common to consider an electric or magnetic dipole that is oscillating in time.

In particular, a harmonically oscillating electric dipole is described by a dipole moment of the form

\mathbf{p}=\mathbf{p'(\mathbf r)}e^{-i\omega t} \, ,

where ω is the angular frequency. In vacuum, this produces fields:

\mathbf{E} = \frac{1}{4\pi\varepsilon_0} \left\{ \frac{\omega^2}{c^2 r} ( \hat{\mathbf{r}} \times \mathbf{p} ) \times \hat{\mathbf{r}} + \left( \frac{1}{r^3} - \frac{i\omega}{cr^2} \right) \left[ 3 \hat{\mathbf{r}} (\hat{\mathbf{r}} \cdot \mathbf{p}) - \mathbf{p} \right] \right\} e^{i\omega r/c}

\mathbf{B} = \frac{\omega^2}{4\pi\varepsilon_0 c^3} \hat{\mathbf{r}} \times \mathbf{p} \left( 1 - \frac{c}{i\omega r} \right) \frac{e^{i\omega r/c}}{r}.

Far away (for \scriptstyle r \omega /c \gg 1), the fields approach the limiting form of a radiating spherical wave:

\mathbf{B} = \frac{\omega^2}{4\pi\varepsilon_0 c^3} (\hat{\mathbf{r}} \times \mathbf{p}) \frac{e^{i\omega r/c}}{r}
\mathbf{E} = c \mathbf{B} \times \hat{\mathbf{r}}

which produces a total time-average radiated power P given by

P = \frac{\omega^4}{12\pi\varepsilon_0 c^3} |\mathbf{p}|^2.

This power is not distributed isotropically, but is rather concentrated around the directions lying perpendicular to the dipole moment. Usually such equations are described by spherical harmonics, but they look very different. A circular polarized dipole is described as a superposition of two linear dipoles.

See also

Notes

  1. Magnetic colatitude is 0 along the dipole's axis and 90° in the plane perpendicular to its axis.
  2. a b δ3(r) = 0 except at r = (0,0,0), so this term is ignored in multipole expansion.

References

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