29/04/14

https ://en.wikipedia.org/wiki/Rigid_rotor

#1

Rigid rotor
From Wikipedia, the free encyclopedia

The rigid rotor is a mechanical model that is used to explain rotating systems. An arbitrary rigid rotor is a 3-dimensional rigid object, such as a top. To orient such an object in space three angles known as Euler angles are required. A special rigid rotor is the linear rotor which requires only two angles to describe its orientation. An example of a linear rotor is a diatomic molecule. More general molecules like water (asymmetric rotor), ammonia (symmetric rotor), or methane (spherical rotor) are 3-dimensional, see classication of molecules.

Contents
1 Linear rotor 1.1 Classical linear rigid rotor 1.2 Quantum mechanical linear rigid rotor 1.3 Selection rules 1.4 Non-rigid linear rotor 2 Arbitrarily shaped rigid rotor 2.1 Coordinates of the rigid rotor 2.2 Classical kinetic energy 2.2.1 Angular velocity form 2.2.2 Lagrange form 2.2.3 Angular momentum form 2.2.4 Hamilton form 2.3 Quantum mechanical rigid rotor 3 Direct experimental observation of molecular rotations 4 See also 5 References 6 General references

Linear rotor
The linear rigid rotor model consists of two point masses located at xed distances from their center of mass. The xed distance between the two masses and the values of the masses are the only characteristics of the rigid model. However, for many actual diatomics this model is too restrictive since distances are usually not completely xed. Corrections on the rigid model can be made to compensate for small variations in the distance. Even in such a case the rigid rotor model is a useful point of departure (zeroth-order model).

Classical linear rigid rotor

The classical linear rotor consists of two point masses distance ) each at a

is independent of time. The kinematics of a linear rigid rotor is usually described by . In the physics convention the coordinates

means of are the co-latitude (zenith) angle orientation of the rotor in space. The kinetic energy

where Scale factors are of importance for quantum mechanical applications since they enter the curvilinear coordinates

The classical Hamiltonian function of the linear rigid rotor is

Quantum mechanical linear rigid rotor

29/04/14

https ://en.wikipedia.org/wiki/Rigid_rotor

#2

Quantum mechanical linear rigid rotor

The linear rigid rotor model can be used in quantum mechanics to predict the rotational energy of a diatomic molecule. The rotational energy depends on the moment of inertia for the system, . In the center of mass reference frame, the moment of inertia is equal to:

where According to Schrdinger equation:

where energy operator corresponds to the

) operator. For the rigid rotor in a eld-free space, the

where . The Laplacian is given above in terms of spherical polar coordinates. The energy operator written in terms of these coordinates is:

This operator appears also in the Schrdinger equation of the hydrogen atom after the radial part is separated o. The eigenvalue equation becomes

The symbol depend on

. Note that the energy does not

is Introducing the

have the same energy .

In the units of

with used for rotational-vibrational spectroscopy . The rotational constant writes the rotor has a minimum).

, a unit that is often . Often one (the value for which the interaction energy of the atoms in

A typical rotational spectrum consists of a series of peaks that correspond to transitions between levels with dierent values of the angular momentum appear at energies corresponding to an integer multiple of .

Selection rules
Rotational transitions of a molecule occur when the molecule absorbs a photon [a particle of a quantized electromagnetic (em) eld]. Depending on the energy of the photon (i.e., the wavelength of the em eld) this transition may be seen as a sideband of a vibrational and/or electronic transition. Pure rotational transitions, in which the vibronic (= vibrational plus electronic) wave function does not change, occur in the microwave region of the electromagnetic spectrum.

Typically, rotational transitions can only be observed when the angular momentum quantum number changes by 1 (

29/04/14

https ://en.wikipedia.org/wiki/Rigid_rotor

#3

Typically, rotational transitions can only be observed when the angular momentum quantum number changes by 1 ( ). This selection rule arises from a rst-order perturbation theory approximation of the time-dependent

A transition occurs if this integral is non-zero. By separating the rotational part of the molecular wavefunction from the . After integration

will result in nonzero values for the dipole transition moment integral. This

) are not completely xed; the bond between the atoms stretches out as the molecule rotates faster (higher values of the

). This frequency is related to the reduced mass

The non-rigid rotor is an acceptably accurate model for diatomic molecules but is still somewhat imperfect. This is because, although the model does account for bond stretching due to rotation, it ignores any bond stretching due to vibrational energy in the bond (anharmonicity in the potential).

Arbitrarily shaped rigid rotor

An arbitrarily shaped rigid rotor is a rigid body of arbitrary shape with its center of mass xed (or in uniform rectilinear motion) in eld-free space R3, so that its energy consists only of rotational kinetic energy (and possibly constant translational energy that can be ignored). A rigid body can be (partially) characterized by the three eigenvalues of its moment of inertia tensor, which are real nonnegative values known as principal moments of inertia . In microwave spectroscopythe spectroscopy based on rotational transitionsone usually classies molecules (seen as rigid rotors) as follows: spherical rotors symmetric rotors oblate symmetric rotors prolate symmetric rotors asymmetric rotors This classication depends on the relative magnitudes of the principal moments of inertia.

Coordinates of the rigid rotor

29/04/14

https ://en.wikipedia.org/wiki/Rigid_rotor

#4

Coordinates of the rigid rotor

Dierent branches of physics and engineering use dierent coordinates for the description of the kinematics of a rigid rotor. In molecular physics Euler angles are used almost exclusively . In quantum mechanical applications it is advantageous to use Euler angles in a convention that is a simple extension of the physical convention of spherical polar coordinates. The rst step is the attachment of a right-handed orthonormal frame (3-dimensional system of orthogonal axes) to the rotor (a body-xed frame ) . This frame can be attached arbitrarily to the body, but often one uses the principal axes framethe normalized eigenvectors of the inertia tensor, which always can be chosen orthonormal, since the tensor is Hermitian. When the rotor possesses a symmetry-axis, it usually coincides with one of the principal axes. It is convenient to choose as body-xed z-axis the highest-order symmetry axis. One starts by aligning the body-xed frame with a space-xed frame (laboratory axes), so that the body-xed x, y, and z axes coincide with the space-xed X, Y, and Z axis. Secondly, the body and its frame are rotated actively over a positive angle -axis. Thirdly, one rotates the body and its frame over a positive angle -axis of the body-xed frame has after these two rotations the longitudinal angle ), both with respect to the space-xed frame. If the rotor were cylindrical symmetric around its -axis, like the linear rigid rotor, its orientation in space would be unambiguously specied at this point. If the body lacks cylinder (axial) symmetry, a last rotation around its necessary to specify its orientation completely . Traditionally the last rotation angle is called The manner as in The total matrix of the three consecutive rotations is the product ) is

convention; it can be shown (in the same convention in which the order of rotations is reversed.

Let of of the body, the body-xed coordinates of

in the body with respect to the body-xed frame. The elements . Upon rotation becomes,

In particular, if

which shows the correspondence with the Knowledge of the Euler angles as function of time rotor. determine the kinematics of the rigid

Classical kinetic energy

The following text forms a generalization of the well-known s pecial cas e of the axis . of an object that rotates around one

It will be assumed from here on that the body-xed frame is a principal axes frame; it diagonalizes the instantaneous inertia tensor

where the Euler angles are time-dependent and in fact determine the time dependence of equation. This notation implies that at with the space-xed frame. the Euler angles are zero, so that at

by the inverse of this

the body-xed frame coincides

The classical kinetic energy T of the rigid rotor can be expressed in dierent ways:

29/04/14

https ://en.wikipedia.org/wiki/Rigid_rotor

#5

The classical kinetic energy T of the rigid rotor can be expressed in dierent ways: as a function of angular velocity in Lagrangian form as a function of angular momentum in Hamiltonian form. Since each of these forms has its use and can be found in textbooks we will present all of them. Angular velocity form As a function of angular velocity T reads,

with

The vector the body-xed frame. It can be shown that velocity equations of motion known as space). Lagrange form Backsubstitution of the expression of derivatives of the Euler angles). In matrix-vector notation, denition of

where

Angular momentum form Often the kinetic energy is written as a function of the (time-independent) quantity . With respect to the body-xed frame it has the components related to the angular velocity,

Since the body-xed frame moves (depends on time) these components are represent components. The kinetic energy is given by

Hamilton form

29/04/14

https ://en.wikipedia.org/wiki/Rigid_rotor

#6

Hamilton form The Hamilton form of the kinetic energy is written in terms of generalized momenta

where it is used that the

with the inverse metric tensor given by

This inverse tensor is needed to obtain the mechanical energy operator of the rigid rotor. The classical Hamiltonian given above can be rewritten to the following expression, which is needed in the phase integral arising in the classical statistical mechanics of rigid rotors,

Quantum mechanical rigid rotor

See also: As usual quantization is performed by the replacement of the generalized momenta by operators that give rst derivatives with respect to its

and similarly for of all three Euler angles, time derivatives of Euler angles, and inertia moments (characterizing the rigid rotor) by a simple dierential operator that does not depend on time or inertia moments and dierentiates to one Euler angle only . The quantization rule is sucient to obtain the operators that correspond with the classical angular momenta. There are two kinds: space-xed and body-xed angular momentum operators. Both are vector operators, i.e., both have three components that transform as vector components among themselves upon rotation of the space-xed and the body-xed frame, respectively . The explicit form of the rigid rotor angular momentum operators is given (but beware, they must be multiplied with commutation relations.

The quantization rule is not sucient to obtain the kinetic energy operator from the classical Hamiltonian. Since

29/04/14

https ://en.wikipedia.org/wiki/Rigid_rotor

#7

The quantization rule is not sucient to obtain the kinetic energy operator from the classical Hamiltonian. Since classically and the inverses of these functions, the position of these trigonometric functions in the classical Hamiltonian is arbitrary . After quantization the commutation does no longer hold and the order of operators and functions in the Hamiltonian (energy operator) becomes a point of concern. Podolsky 1928 that the energy operator. This operator has the general form (summation convention: sum over repeated indicesin this case over the three Euler angles

where

Given the inverse of the metric tensor above, the explicit form of the kinetic energy operator in terms of Euler angles follows by simple substitution. (Note: The corresponding eigenvalue equation gives the for the rigid rotor in the form that it was solved for the rst time by Kronig and Rabi This is one of the few cases where the Schrdinger equation can be solved analytically . All these cases were solved within a year of the formulation of the Schrdinger equation.) Nowadays it is common to proceed as follows. It can be shown that can be expressed in body-xed angular momentum operators (in this proof one must carefully commute dierential operators with trigonometric functions). The result has the same appearance as the classical formula expressed in body-xed coordinates,

The action of the

so that the Schrdinger equation for the spherical rotor ( degenerate energy equal to The symmetric top (= symmetric rotor) is characterized by In the latter case we write the Hamiltonian as .

and use that

Hence

The eigenvalue eigenvalue. The energies with |k| > 0 are the symmetric top was rst found in 1927. The asymmetric top problem (

have the same -fold degenerate. This exact solution of the Schrdinger equation of

Direct experimental observation of molecular rotations

For long time, molecular rotations could not be directly observed experimentally . Only measurement techniques with [4][5] atomic resolution made it possible to detect the rotation of a single molecule. At low temperatures, the rotations of molecules (or part thereof) can be frozen. This could be directly visualized by Scanning tunneling microscopy i.e., the stabilization could be explained at higher temperatures the rotational entropy . [5]

29/04/14

https ://en.wikipedia.org/wiki/Rigid_rotor

#8

See also
Balancing machine Gyroscope Infrared spectroscopy Rigid body Rotational spectroscopy Spectroscopy Vibrational spectroscopy Quantum rotor model

References
1. ^ a b Podols ky, B. (1928). Phys. Rev. 32 : 812. Bibcode:1928PhRv...32...812J (http://ads abs .harvard.edu/abs /1928PhRv...32...812J). doi:10.1103/Phys Rev.32.812 (http://dx.doi.org/10.1103%2FPhys Rev.32.812). 2. ^ Chapter 4.9 of Golds tein, H.; Poole, C. P.; Safko, J. L. (2001). Clas s ical Mechanics (Third ed.). San Francis co: Addis on W es ley Publis hing Company . ISBN 0-201-65702-3. 3. ^ a b R. de L. Kronig and I. I. Rabi (1927). "The Symmetrical Top in the Undulatory Mechanics ". Phys. Rev. 29 : 262269. Bibcode:1927PhRv...29..262K (http://ads abs .harvard.edu/abs /1927PhRv...29..262K). doi:10.1103/Phys Rev.29.262 (http://dx.doi.org/10.1103%2FPhys Rev.29.262). 4. ^ J. K. Gimzews ki, C. Joachim, R. R. Schlittler, V. Langlais , H. Tang, I. Johanns en (1998), "Rotation of a Single Molecule Within a Supramolecular Bearing" (in German), Science 281 (5376): pp.531533, doi:10.1126/s cience.281.5376.531 (http://dx.doi.org/10.1126%2Fs cience.281.5376.531) 5. ^ a b Thomas W aldmann, Jens Klein, Harry E. Hos ter, R. Jrgen Behm (2012), "Stabilization of Large Ads orbates by Rotational Entropy: A Time-Res olved Variable-Temperature STM Study" (in German), ChemPhysChem: pp.n/an/a, doi:10.1002/cphc.201200531 (http://dx.doi.org/10.1002%2Fcphc.201200531)

General references
D. M. Dennison (1931). "The Infrared Spectra of Polyatomic Molecules Part I". Rev. Mod. Physics 3: 280345. Bibcode:1931RvMP....3..280 D (http://adsabs.harvard.edu/abs/1931RvMP....3..280 D). doi:10.1103/RevModPhys.3.280 (http://dx.doi.org/10.1103%2FRevModPhys.3.280) . (Especially Section 2: The Rotation of Polyatomic Molecules). Van Vleck, J. H. (1951). "The Coupling of Angular Momentum Vectors in Molecules". Rev. Mod. Physics 23: 213227. Bibcode:1951RvMP...23..213 V (http://adsabs.harvard.edu/abs/1951RvMP...23..213 V). doi:10.1103/RevModPhys.23.213 (http://dx.doi.org/10.1103%2FRevModPhys.23.213) . McQuarrie, Donald A (1983). Quantum Chemistry. Mill Valley, Calif.: University Science Books. ISBN0-935702-13-X. Goldstein, H.; Poole, C. P.; Safko, J. L. (2001). Classical Mechanics (Third ed.). San Francisco: Addison Wesley Publishing Company . ISBN0-201-65702-3. (Chapters 4 and 5) Arnold, V. I. (1989). Mathematical Methods of Classical Mechanics. Springer-Verlag. ISBN0-387-96890-3. (Chapter 6). Kroto, H. W. (1992). Molecular Rotation Spectra . New York: Dover. Gordy, W.; Cook, R. L. (1984). Microwave Molecular Spectra (Third ed.). New York: Wiley . ISBN0-471-08681-9. Papouek, D.; Aliev, M. T. (1982). Molecular Vibrational-Rotational Spectra . Amsterdam: Elsevier. ISBN0-444-99737-7. Retrieved from "http://en.wikipedia.org/w/index.php?title=Rigid_rotor&oldid=569453221" Categories: Molecular physics Rigid bodies Rotation This page was last modied on 20 August 2013 at 18:33. Text is available under the Creative Commons Attribution-ShareAlike License; additional terms may apply . By using this site, you agree to the Terms of Use and Privacy Policy. Wikipedia is a registered trademark of the Wikimedia Foundation, Inc., a non-prot organization.