Harmonic oscillator potential

An important property of the time autocorrelation function CaU) is that by taking its Fourier transform, F CA(t) a, one gets a spectral decomposition of all the frequencies that contribute to the motion. For example, consider the motion of a single particle in a hannonic potential (harmonic oscillator). The time series describing the position of the... 

Fig. 1. Optimization of the Onsager-Machlup action for the two dimensional harmonic oscillator. The potential energy is U(x,y) = 25i/ ), the mass is 1...

Most of the molecules we shall be interested in are polyatomic. In polyatomic molecules, each atom is held in place by one or more chemical bonds. Each chemical bond may be modeled as a harmonic oscillator in a space defined by its potential energy as a function of the degree of stretching or compression of the bond along its axis (Fig. 4-3). The potential energy function V = kx j2 from Eq. (4-8), or W = ki/2) ri — riof in temis of internal coordinates, is a parabola open upward in the V vs. r plane, where r replaces x as the extension of the rth chemical bond. The force constant ki and the equilibrium bond distance riQ, unique to each chemical bond, are typical force field parameters. Because there are many bonds, the potential energy-bond axis space is a many-dimensional space. 

Figure 4-3 Potential Energy as a Function of Compression or Stretching of a One-Dimensional Harmonic Oscillator.

The Morse oscillator model is often used to go beyond the harmonic oscillator approximation. In this model, the potential Ej(R) is expressed in terms of the bond dissociation energy Dg and a parameter a related to the second derivative k of Ej(R) at Rg k = ( d2Ej/dR2) = 2a2Dg as follows ... 

Bond stretching is most often described by a harmonic oscillator equation. It is sometimes described by a Morse potential. In rare cases, bond stretching will be described by a Leonard-Jones or quartic potential. Cubic equations have been used for describing bond stretching, but suffer from becoming completely repulsive once the bond has been stretched past a certain point. 

Figure 1.13 Plot of potential energy, V(r), against bond length, r, for the harmonic oscillator model for vibration is the equilibrium bond length. A few energy levels (for v = 0, 1, 2, 3 and 28) and the corresponding wave functions are shown A and B are the classical turning points on the wave function for w = 28...

The reason that does not change with isotopic substitution is that it refers to the bond length at the minimum of the potential energy curve (see Figure 1.13), and this curve, whether it refers to the harmonic oscillator approximation (Section 1.3.6) or an anharmonic oscillator (to be discussed in Section 6.1.3.2), does not change with isotopic substitution. Flowever, the vibrational energy levels within the potential energy curve, and therefore tq, are affected by isotopic substitution this is illustrated by the mass-dependence of the vibration frequency demonstrated by Equation (1.68). 

Figure 1.13 shows the potential function, vibrational wave functions and energy levels for a harmonic oscillator. Just as for rotation it is convenient to use term values instead of energy levels. Vibrational term values G(v) invariably have dimensions of wavenumber, so we have, from Equation (1.69),... 

Figure 6.4 Potential energy curve and energy levels for a diatomic molecule behaving as an anharmonic oscillator compared with those for a harmonic oscillator (dashed curve)...

Owing to the effects of mechanical anharmonicity - to which we shall refer in future simply as anharmonicity since we encounter electrical anharmonicity much less frequently -the vibrational wave functions are also modified compared wifh fhose of a harmonic oscillator. Figure 6.6 shows some wave functions and probabilify densify functions (iA A ) for an anharmonic oscillator. The asymmefry in and (iA A ) 5 compared wifh fhe harmonic oscillator wave functions in Figure f.i3, increases fheir magnitude on the shallow side of the potential curve compared with the steep side. 

According to (2.29), dissipation reduces the spread of the harmonic oscillator making it smaller than the quantum uncertainty of the position of the undamped oscillator (de Broglie wavelength). Within exponential accuracy (2.27) agrees with the Caldeira-Leggett formula (2.26), and similar expressions may be obtained for more realistic potentials. 

The corresponding level broadening equals half. In fact is the diagonal kinetic coefficient characterizing the rate of phonon-assisted escape from the ground state [Ambegaokar 1987]. In harmonic approximation for the well the only nonzero matrix element is that with /= 1,K0 Q /> = <5o, where is the zero-point spread of the harmonic oscillator. For an anharmonic potential, other matrix elements contribute to (2.52). 

Consider a potential like that in fig. 19. In the vicinity of the parabolic well (t -> 0) at )S > (Oq the instanton solution (3.34), corresponding to a harmonic oscillator in imaginary time, is given by... 

It is left to reader to verify that, under Lee .s discrete mechanics, both free particles and particles subjected to a constant force, behave in essentially the sa e way as they do under continuous equations of motion. Moreover, the time intervals At = t-i i — ti are all equal. While the spatial behavior for non-constant forces (ex particles in a harmonic oscillator V potential) also remains essentially... 

Exercise 3.4. Evaluate the free-energy difference between two one-dimensional harmonic oscillators with potentials U1 = (X- l)2 and U2 = 0.3(X —... 

The sequence of levels shown in Figure 2 closely resembles the level diagram found by Mayer and Jensen by analysis of observed nuclear properties, with the help of the calculated level sequences for harmonic-oscillator and square-well potential func-... 

The isotopic difference between the mean squares of the displacements in equation (7) can be calculated if the carbon-hydrogen oscillator is treated as a diatomic molecule. It is easily shown that for constant potential the mean square of the displacement from the equilibrium position of the harmonic oscillator will be inversely proportional to the square root of the reduced mass, /x, and hence... 

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