Rigid rotor

In classical mechanics, 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 are required. A special rigid rotor is the linear rotor which is a 2-dimensional object, requiring two angles to describe its orientation.

In molecular physics, a molecule can often be regarded as a rigid rotor. An example is a diatomic molecule in its vibrational ground state. In most diatomics the vibrational motion is fairly stiff, i.e., its vibrational excitation energies are very high compared to its rotational excitation energies. If one neglects vibration all together, the diatomic molecule becomes a rigid linear rotor. More general molecules, too, can often be seen as rigid. Rigid rotors can be classified by means of their inertia moments, see classification of rigid rotors. For instance the water molecule (H₂O) is an asymmetric rotor, the ammonia molecule (NH₃) is a symmetric rotor, and methane (CH₄) is spherical rotor.

The linear rotor

The classical as well as the quantum mechanical linear rigid rotor model consists of two point masses located at fixed distances from their center of mass. The fixed distance between the two point masses and the values of the masses are the only characteristics of the rigid model.

The classical linear rigid rotor

The two point masses are denoted by m₁ and m₂ [with reduced mass μ ≡ m₁ m₂/(m₁ + m₂)] and are kept at a fixed distance R. Classically, the rotor is rigid if R is independent of time. The kinematics of a linear rigid rotor is usually described by means of spherical polar coordinates, which form a coordinate system of 3-dimensional space. In the physics convention the coordinates are the colatitude (zenith) angle θ, the longitudinal (azimuth) angle φ and the distance R. The angles specify the orientation of the rotor in space. The kinetic energy T of the linear rigid rotor in Lagrangian form (in terms of coordinates and time derivatives of coordinates) is:

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle 2T = \mu R^2\big [\dot{\theta}^2+(\dot\varphi\,\sin\theta)^2\big]. }

The classical Hamiltonian function of the linear rigid rotor is:

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle H = \frac{1}{2\mu R^2}\left[p^2_{\theta} + \frac{p^2_{\varphi}}{\sin^2\theta}\right]. }

It is possible to write the Lagrangian in matrix form:

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle 2T = \mu R^2 \big(\dot{\theta}\;\; \dot{\varphi} \Big) \begin{pmatrix} 1 & 0 \\ 0 & \sin^2 \theta \\ \end{pmatrix} \begin{pmatrix} \dot{\theta}\\ \dot{\varphi} \end{pmatrix} = \mu \Big(\dot{\theta}\;\; \dot{\varphi} \Big) \begin{pmatrix} h_\theta^2 & 0 \\ 0 & h_\varphi^2 \\ \end{pmatrix} \begin{pmatrix} \dot{\theta}\\ \dot{\varphi} \end{pmatrix}, }

where h_θ ≡ R and h_φ ≡ Rsinθ are scale (or Lamé) factors.

Scale factors are of importance for quantum mechanical applications since they enter the Laplacian expressed in curvilinear coordinates. In the case at hand (constant R)

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \nabla^2 = \frac{1}{h_\theta h_\varphi}\left[ \frac{\partial}{\partial \theta} \frac{h_\varphi}{h_\theta} \frac{\partial}{\partial \theta} +\frac{\partial}{\partial \varphi} \frac{h_\theta}{h_\varphi} \frac{\partial}{\partial \varphi} \right]= \frac{1}{R^2}\left[\frac{1}{\sin\theta} \frac{\partial}{\partial \theta} \sin\theta \frac{\partial}{\partial \theta} +\frac{1}{\sin^2\theta}\frac{\partial^2}{\partial \varphi^2} \right]. }

The 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, I. In the center of mass reference frame, the moment of inertia is equal to:

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle I = \mu R^2\,}

where μ is the reduced mass of the molecule and R is the distance between the two atoms.

According to quantum mechanics, the energy levels of a system can be determined by solving the Schrödinger equation H Ψ = E Ψ, where Ψ is the wave function and H is the energy (Hamiltonian) operator. For the rigid rotor in a field-free space, the energy operator corresponds to the kinetic energy of the system:

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \hat H = - \frac{\hbar^2}{2\mu} \nabla^2,}

where Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \hbar} is Planck's constant divided by Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle 2\pi} and Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \nabla^2} is the Laplacian. The Laplacian is given above in terms of spherical polar coordinates. The energy operator written in terms of these coordinates is:

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \hat H =- \frac{\hbar^2}{2I} \left [ {1 \over \sin \theta} {\partial \over \partial \theta} \left ( \sin \theta {\partial \over \partial \theta} \right ) + {1 \over {\sin^2 \theta}} {\partial^2 \over \partial \varphi^2} \right].}

This operator appears also in the (θ, φ)-part of the Schrödinger equation of the hydrogen-like atoms,

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \hat{H} = \frac{\hat{l}^2}{2\mu R^2} = \frac{\hat{l}^2}{2I}\quad\hbox{with}\quad \hat{l}^2 = -\hbar^2 \left [ {1 \over \sin \theta} {\partial \over \partial \theta} \left ( \sin \theta {\partial \over \partial \theta} \right ) + {1 \over {\sin^2 \theta}} {\partial^2 \over \partial \varphi^2} \right]. }

The eigenvalue equation becomes

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \tfrac{1}{2I}\; \hat{l}^2\;Y_\ell^m(\theta, \varphi ) = \tfrac{1}{2I}\; \hbar^2\ell(\ell+1) \;Y_\ell^m(\theta, \varphi ). }

Here Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Y_\ell^m (\theta, \varphi )} represents a set of functions known as the spherical harmonics. Note that the energy does not depend on Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle m \,} . The energy

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle E_\ell \equiv {\hbar^2 \over 2I} \ell \left (\ell+1\right ) }

is Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle 2\ell+1} -fold degenerate: the functions with fixed Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \ell\,} and Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle m=-\ell,-\ell+1,\dots,\ell} have the same energy.

In microwave spectroscopy one prefers using the rotational constant B instead of the inertia moment, and one writes,

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle E_\ell = B\; \ell \left (\ell+1\right )\quad \textrm{with}\quad B \equiv \frac{\hbar^2}{2I}. }

In the unit of reciprocal length the rotational constant is,

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \bar B \equiv \frac{B}{hc} = \frac{h}{8\pi^2cI}, }

with c the speed of light. If cgs units are used for h, c, and I, Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \bar B} is expressed in wave numbers, cm^-1, a unit that is often used in rotational-vibrational spectroscopy.

Obviously, the rotational constant Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \bar B} depends on the distance R. Often one writes Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle B_e = \bar B(R_e) } where R_e is the equilibrium value of R (the value for which the interaction energy of the atoms in the rotor has a minimum).

Arbitrarily shaped rigid rotor

An arbitrarily shaped rigid rotor is a rigid body of arbitrary shape with its center of mass fixed (or in uniform rectilinear motion) in field-free space Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle {\scriptstyle \mathbb{R}^3}} , so that its energy consists only of rotational kinetic energy (plus possibly a 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 spectroscopy—the spectroscopy based on rotational transitions—one usually classifies molecules (seen as rigid rotors) as follows:

• spherical rotors
• symmetric rotors
  • oblate symmetric rotors
  • prolate symmetric rotors
• asymmetric rotors

This classification depends on the relative magnitudes of the principal moments of inertia.

Coordinates of the rigid rotor

Different branches of physics and engineering use different 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 spherical polar angles.

The first step is the attachment of a right-handed orthonormal frame (3-dimensional system of orthogonal axes) to the rotor (a body-fixed frame) . This frame can be attached arbitrarily to the body, but often one uses the principal axes frame—the normalized eigenvectors of the inertia tensor, which always can be chosen orthonormal, since the tensor is symmetric. When the rotor possesses a symmetry-axis, it usually coincides with one of the principal axes. It is convenient to choose as body-fixed z-axis the highest-order symmetry axis.

One starts by aligning the body-fixed frame with a space-fixed frame (laboratory axes), so that the body-fixed x, y, and z axes coincide with the space-fixed X, Y, and Z axis. Then the body and its frame are rotated actively over a positive angle α around the z-axis (by the right-hand rule), which moves the Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle y} - to the Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle y'} -axis. Thirdly, one rotates the body and its frame over a positive angle β around the Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle y'} -axis. The z-axis of the body-fixed frame has after these two rotations the longitudinal angle α (commonly designated by φ) and the colatitude angle β (commonly designated by θ), both with respect to the space-fixed frame. If the rotor were cylindrical symmetric around its body-fixed z-axis, like the linear rigid rotor, its orientation in space would be unambiguously specified at this point.

If the body lacks cylinder (axial) symmetry, a last rotation around its z-axis (which has polar coordinates β and α) is necessary to specify its orientation completely. Traditionally the last rotation angle is called γ.

The convention for Euler angles described here is known as the Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle z''-y'-z} convention; it can be shown (in the same manner as in this article) that it is equivalent to the Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle z-y-z} convention in which the order of rotations is reversed.

The total matrix of the three consecutive rotations is the product

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \mathbf{R}(\alpha,\beta,\gamma)= \begin{pmatrix} \cos\alpha & -\sin\alpha & 0 \\ \sin\alpha & \cos\alpha & 0 \\ 0 & 0 & 1 \end{pmatrix} \begin{pmatrix} \cos\beta & 0 & \sin\beta \\ 0 & 1 & 0 \\ -\sin\beta & 0 & \cos\beta \\ \end{pmatrix} \begin{pmatrix} \cos\gamma & -\sin\gamma & 0 \\ \sin\gamma & \cos\gamma & 0 \\ 0 & 0 & 1 \end{pmatrix} }

Let r(0) be the coordinate vector with respect to the body-fixed frame of an arbitrary point ℘ of the body. We call the three elements of r(0) the "body-fixed coordinates" of ℘. Initially r(0) is also the space-fixed coordinate vector of ℘. Upon rotation of the body (including its frame and its point ℘), the body-fixed coordinates of ℘ do not change, but the space-fixed coordinate vector of ℘ becomes,

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \mathbf{r}(\alpha,\beta,\gamma)= \mathbf{R}(\alpha,\beta,\gamma)\mathbf{r}(0). }

In particular, if ℘ is initially on the space-fixed Z-axis, it has the space-fixed coordinates

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \mathbf{R}(\alpha,\beta,\gamma) \begin{pmatrix} 0 \\ 0 \\ r \\ \end{pmatrix}= \begin{pmatrix} r \cos\alpha\sin\beta \\ r \sin\alpha \sin\beta \\ r \cos\beta \\ \end{pmatrix}, }

which shows the correspondence with the spherical polar coordinates (in the physical convention).

Knowledge of the Euler angles as function of time t and the initial coordinate vector r(0) determine the kinematics of the rigid rotor.

Classical kinetic energy

The following is a generalization of the well-known special case of the rotational energy of an object that rotates around one axis.

It will be assumed from here on that the body-fixed frame is a principal axes frame; it diagonalizes the instantaneous inertia tensor Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \mathbf{I}(t)} (expressed with respect to the space-fixed frame), i.e.,

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \mathbf{R}(\alpha,\beta,\gamma)^{-1}\; \mathbf{I}(t)\; \mathbf{R}(\alpha,\beta,\gamma) = \mathbf{I}(0)\quad\hbox{with}\quad \mathbf{I}(0) = \begin{pmatrix} I_1 & 0 & 0 \\ 0 & I_2 & 0 \\ 0 & 0 & I_3 \\ \end{pmatrix}, }

where the Euler angles are time-dependent and in fact determine the time dependence of Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \mathbf{I}(t)} by the inverse of this equation. This notation implies that at Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle t=0} the Euler angles are zero, so that at Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle t=0} the body-fixed frame coincides with the space-fixed frame.

The classical kinetic energy T of the rigid rotor can be expressed in different 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,

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle T = \frac{1}{2} \left[ I_1 \omega_x^2 + I_2 \omega_y^2+ I_3 \omega_z^2 \right] }

with

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \begin{pmatrix} \omega_x \\ \omega_y \\ \omega_z \\ \end{pmatrix} = \begin{pmatrix} -\sin\beta\cos\gamma & \sin\gamma & 0 \\ \sin\beta\sin\gamma & \cos\gamma & 0 \\ \cos\beta & 0 & 1 \\ \end{pmatrix} \begin{pmatrix} \dot{\alpha} \\ \dot{\beta} \\ \dot{\gamma} \\ \end{pmatrix}. }

The vector ω = (ω_x, ω_y, ω_z) contains the components of the angular velocity of the rotor expressed with respect to the body-fixed frame. It can be shown that ω is not the time derivative of any vector, in contrast to the usual definition of velocity. The dots over the time-dependent Euler angles indicate time derivatives.

Lagrange form

Backsubstitution of the expression of ω into T gives the kinetic energy in Lagrange form (as a function of the time derivatives of the Euler angles). In matrix-vector notation,

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle 2 T = \begin{pmatrix} \dot{\alpha} & \dot{\beta} & \dot{\gamma} \end{pmatrix} \; \mathbf{g} \; \begin{pmatrix} \dot{\alpha} \\ \dot{\beta} \\ \dot{\gamma}\\ \end{pmatrix}, }

where Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \mathbf{g}} is the metric tensor associated with Euler angles—a non-orthogonal system of curvilinear coordinates—

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \mathbf{g}= \begin{pmatrix} I_1 \sin^2\beta \cos^2\gamma+I_2\sin^2\beta\sin^2\gamma+I_3\cos^2\beta & (I_2-I_1) \sin\beta\sin\gamma\cos\gamma & I_3\cos\beta \\ (I_2-I_1) \sin\beta\sin\gamma\cos\gamma & I_1\sin^2\gamma+I_2\cos^2\gamma & 0 \\ I_3\cos\beta & 0 & I_3 \\ \end{pmatrix}. }

Angular momentum form

Often the kinetic energy is written as a function of the angular momentum Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \vec{L}} of the rigid rotor. This vector is a conserved (time-independent) quantity. With respect to the body-fixed frame it has the components Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \mathbf{L}} , which can be shown to be related to the angular velocity,

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \mathbf{L} = \mathbf{I}(0)\; \boldsymbol{\omega}\quad\hbox{or}\quad L_i = \frac{\partial T}{\partial\omega_i},\;\; i=x,\,y,\,z. }

Since the body-fixed frame moves (depends on time) these components are not time independent. If we were to represent Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \vec{L}} with respect to the stationary space-fixed frame, we would find time independent expressions for its components. The kinetic energy is given by

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle T = \frac{1}{2} \left[ \frac{L_x^2}{I_1} + \frac{L_y^2}{I_2}+ \frac{L_z^2}{I_3}\right]. }

Hamilton form

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

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \begin{pmatrix} p_\alpha \\ p_\beta \\ p_\gamma \\ \end{pmatrix} \ \stackrel{\mathrm{def}}{=}\ \begin{pmatrix} \partial T/{\partial \dot{\alpha}}\\ \partial T/{\partial \dot{\beta}} \\ \partial T/{\partial \dot{\gamma}} \\ \end{pmatrix} = \mathbf{g} \begin{pmatrix} \; \, \dot{\alpha} \\ \dot{\beta} \\ \dot{\gamma}\\ \end{pmatrix}, }

where it is used that the Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \mathbf{g}} is symmetric. In Hamilton form the kinetic energy is,

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle 2 T = \begin{pmatrix} p_{\alpha} & p_{\beta} & p_{\gamma} \end{pmatrix} \; \mathbf{g}^{-1} \; \begin{pmatrix} p_{\alpha} \\ p_{\beta} \\ p_{\gamma}\\ \end{pmatrix}, }

with the inverse metric tensor given by

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle {\scriptstyle \sin^2\beta}\;\;\mathbf{g}^{-1}= }

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \begin{pmatrix} \frac{\cos^2\gamma}{I_1}+\frac{\sin^2\gamma}{I_2} & \left(\frac{1}{I_2}-\frac{1}{I_1}\right){\scriptstyle \sin\beta\sin\gamma\cos\gamma}& -\frac{\cos\beta\cos^2\gamma}{I_1}-\frac{\cos\beta\sin^2\gamma}{I_2} \\ \left(\frac{1}{I_2}-\frac{1}{I_1}\right){\scriptstyle \sin\beta\sin\gamma\cos\gamma}& \frac{\sin^2\beta\sin^2\gamma}{I_1}+\frac{\sin^2\beta\cos^2\gamma}{I_2} & \left(\frac{1}{I_1}-\frac{1}{I_2}\right){\scriptstyle \sin\beta\cos\beta\sin\gamma\cos\gamma}\\ -\frac{\cos\beta\cos^2\gamma}{I_1}-\frac{\cos\beta\sin^2\gamma}{I_2} & \left(\frac{1}{I_1}-\frac{1}{I_2}\right){\scriptstyle \sin\beta\cos\beta\sin\gamma\cos\gamma} & \frac{\cos^2\beta\cos^2\gamma}{I_1}+ \frac{\cos^2\beta\sin^2\gamma}{I_2}+\frac{\sin^2\beta}{I_3} \\ \end{pmatrix}. }

This inverse tensor is needed to obtain the Laplace-Beltrami operator, which (multiplied by Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle -\hbar^2} ) gives the quantum 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,

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \begin{array}{lcl} T &=& \frac{1}{2I_1 \sin^2\beta} \left( (p_\alpha- p_\gamma\cos\beta)\cos\gamma -p_\beta \sin\beta\sin\gamma \right)^2 \\ &&+ \frac{1}{2I_2 \sin^2\beta} \left( (p_\alpha- p_\gamma\cos\beta)\sin\gamma +p_\beta \sin\beta\cos\gamma \right)^2 + \frac{p_\gamma^2}{2I_3}. \\ \end{array} }

Quantum mechanical rigid rotor

As usual quantization is performed by the replacement of the generalized momenta by operators that give first derivatives with respect to its canonically conjugate variables (positions). Thus,

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle p_\alpha \longrightarrow -i \hbar \frac{\partial}{\partial \alpha} }

and similarly for Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle p_\beta} and Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle p_\gamma} . It is remarkable that this rule replaces the fairly complicated function Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle p_\alpha} of all three Euler angles, time derivatives of Euler angles, and inertia moments (characterizing the rigid rotor) by a simple differential operator that does not depend on time or inertia moments and differentiates to one Euler angle only.

The quantization rule is sufficient to obtain the operators that correspond with the classical angular momenta. There are two kinds: space-fixed and body-fixed 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-fixed and the body-fixed frame, respectively. The explicit form of the rigid rotor angular momentum operators is given here (but beware, they must be multiplied with Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \hbar} ). The body-fixed angular momentum operators are written as Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \hat{\mathcal{P}}_i} . They satisfy anomalous commutation relations.

The quantization rule is not sufficient to obtain the kinetic energy operator from the classical Hamiltonian. Since classically Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle p_\beta} commutes with Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \cos\beta} and Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \sin\beta} and the reciprocals of these functions, the position of these trigonometric functions in the classical Hamiltonian is arbitrary. After quantization the commutation no longer holds and the order of operators and functions in the Hamiltonian (energy operator) becomes a point of concern. Podolsky proposed in 1928 that the Laplace-Beltrami operator (times Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle -\tfrac{1}{2}\hbar^2} ) has the appropriate form for the quantum mechanical kinetic energy operator. This operator has the general form (summation convention: sum over repeated indices—in this case over the three Euler angles q¹ ≡ α, q² ≡ β, q³ ≡ γ),

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \hat{H} = - \tfrac{\hbar^2}{2}\;|g|^{-1/2} \frac{\partial}{\partial q^i} |g|^{1/2} g^{ij} \frac{\partial}{\partial q^j}, }

where Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle |g|} is the determinant of the g-tensor:

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle |g| = I_1\, I_2\, I_3\, \sin^2 \beta \quad \hbox{and}\quad g^{ij} = (\mathbf{g}^{-1})_{ij}. }

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.

It can be shown that Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \hat{H}} can be expressed in body-fixed angular momentum operators (in this proof one must carefully commute differential operators with trigonometric functions). The result has the same appearance as the classical formula expressed in body-fixed coordinates,

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \hat{H} = \tfrac{1}{2}\left[ \frac{\mathcal{P}_x^2}{I_1}+ \frac{\mathcal{P}_y^2}{I_2}+ \frac{\mathcal{P}_z^2}{I_3} \right]. }

The action of the Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \hat{\mathcal{P}}_i} on the Wigner D-matrix is simple. In particular

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \mathcal{P}^2\, D^j_{m'm}(\alpha,\beta,\gamma)^* = \hbar^2 j(j+1) D^j_{m'm}(\alpha,\beta,\gamma)^* \quad\hbox{with}\quad \mathcal{P}^2= \mathcal{P}^2_x + \mathcal{P}_y^2+ \mathcal{P}_z^2, }

so that the Schrödinger equation for the spherical rotor (I₁ = I₂ = I₃) is solved with the (2j+1)² degenerate energy equal to Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \tfrac{\hbar^2 j(j+1)}{2I}} and Wigner D-matrix elements as eigenfunctions.

Schrödinger equation for symmetric top

The symmetric top (= symmetric rotor) is characterized by two equal principal moments of inertia. It is a prolate (cigar shaped) top if I₃ < I₁ = I₂. In this case we write the Hamiltonian as

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \hat{H} = \tfrac{1}{2}\left[ \frac{\mathcal{P}^2}{I_1}+ \mathcal{P}_z^2\Big(\frac{1}{I_3} -\frac{1}{I_1} \Big) \right]. }

Introducing the angular momentum operators in their differential operator form, we obtain the Schrödinger equation as it was solved for the first time by Kronig and Rabi. The symmetric top is one of the few cases where the Schrödinger equation can be solved analytically. All these cases were solved within a year of the formulation of the Schrödinger equation.

Knowing today the form of the Hamiltonian in terms of angular momentum operators, we can use

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \mathcal{P}_z^2\, D^j_{m k}(\alpha,\beta,\gamma)^* = k^2\, D^j_{m k}(\alpha,\beta,\gamma)^*. }

Hence

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \hat{H}\,D^j_{m k}(\alpha,\beta,\gamma)^* = E_{jk} D^j_{m k}(\alpha,\beta,\gamma)^* \quad \hbox{with}\quad E_{jk} = \frac{j(j+1)}{2I_1} + k^2\left(\frac{1}{2I_3}-\frac{1}{2I_1}\right). }

The eigenvalue E_j0 is (2j + 1)-fold degenerate, for all eigenfunctions with m = − j, −j + 1, ..., j have the same eigenvalue. The energies with |k| > 0 are 2(2j + 1)-fold degenerate.

The asymmetric top problem ($I_{1}\neq I_{2}\neq I_{3}$) is not exactly soluble.

References

Cited references

General references

• D. M. Dennison, Rev. Mod. Physics, vol. 3, pp. 280-345, (1931) (Especially Section 2: The Rotation of Polyatomic Molecules).
• J. H. Van Vleck, Rev. Mod. Physics, vol. 23, pp. 213-227 (1951).
• McQuarrie, Donald A (1983). Quantum Chemistry. Mill Valley, Calif.: University Science Books. ISBN 0-935702-13-X. 
• H. Goldstein, C. P. Poole, J. L. Safko, Classical Mechanics, Third Ed., Addison Wesley Publishing Company, San Francisco (2001) ISBN 0-201-65702-3. (Chapters 4 and 5)
• V. I. Arnold, Mathematical Methods of Classical Mechanics, Springer-Verlag (1989), ISBN 0-387-96890-3. (Chapter 6).
• H. W. Kroto, Molecular Rotation Spectra, Dover Inc., New York, (1992).
• W. Gordy and R. L. Cook, Microwave Molecular Spectra, Third Ed., Wiley, New York (1984).
• D. Papoušek and M. T. Aliev, Molecular Vibrational-Rotational Spectra, Elsevier, Amsterdam (1982).