Energy, zero-point

Here the zero point energy is temporarily suppressed. Now the exponential is a product of independent factors. Thus one gets... 

This is the Planck distribution function. The themial average energy in theyth mode is (including the zero point energy)... 

Flere the zero point energy is ignored, which is appropriate at reasonably large temperatures when the average occupation number is large. In such a case one can also replace the sum over by an integral. Each of the triplet n can take the values 0, 1, 2,. . ., co. Thus the sum over can be replaced by an... 

The constant of integration is zero at zero temperature all the modes go to the unique non-degenerate ground state corresponding to the zero point energy. For this state S log(g) = log(l) = 0, a confmnation of the Third Law of Thennodynamics for the photon gas. 

The activation energy, is defined as tlie minimum additional energy above the zero-point energy that is needed for a system to pass from the initial to the final state in a chemical reaction. In tenns of equation (A2.4.132). the energy of the initial reactants at v = v is given by... 

Figure A3.13.il. Illustration of the time evolution of redueed two-dimensional probability densities I I and I I for the exeitation of CHD between 50 and 70 fs (see [154] for further details). The full eurve is a eut of tire potential energy surfaee at the momentary absorbed energy eorresponding to 3000 em during the entire time interval shown here (as6000 em, if zero point energy is ineluded). The dashed eurves show the energy uneertainty of the time-dependent wave paeket, approximately 500 em Left-hand side exeitation along the v-axis (see figure A3.13.5). The vertieal axis in the two-dimensional eontour line representations is...

Figure B3.4.1. The potential surfaee for the eollinear D + H2 DH + H reaetion (this potential is the same as for H + H2 — H2 + H, but to make the produets and reaetants identifieation elearer the isotopieally substituted reaetion is used). The D + H2 reaetant arrangement and the DH + H produet arrangement are denoted. The eoordinates are r, the H2 distanee, and R, the distanee between the D and the H2 eentre of mass. Distanees are measured in angstroms the potential eontours shown are 4.7 eV-4.55 eV,.. ., -3.8 eV. (The potential energy is zero when the partieles are far from eaeh other. Only the first few eontours are shown.) For referenee, the zero-point energy for H2 is -4.47 eV, i.e. 0.27 eV above the H2 potential minimum (-4.74 eV) the room-temperature thennal kinetie energy is approximately 0.03 eV. The graph uses the aeeiirate Liu-Seigbalm-Triihlar-Horowitz (LSTH) potential surfaee [195].

Rare-gas clusters can be produced easily using supersonic expansion. They are attractive to study theoretically because the interaction potentials are relatively simple and dominated by the van der Waals interactions. The Lennard-Jones pair potential describes the stmctures of the rare-gas clusters well and predicts magic clusters with icosahedral stmctures [139, 140]. The first five icosahedral clusters occur at 13, 55, 147, 309 and 561 atoms and are observed in experiments of Ar, Kr and Xe clusters [1411. Small helium clusters are difficult to produce because of the extremely weak interactions between helium atoms. Due to the large zero-point energy, bulk helium is a quantum fluid and does not solidify under standard pressure. Large helium clusters, which are liquid-like, have been produced and studied by Toennies and coworkers [142]. Recent experiments have provided evidence of... 

After transforming to Cartesian coordinates, the position and velocities must be corrected for anharmonicities in the potential surface so that the desired energy is obtained. This procedure can be used, for example, to include the effects of zero-point energy into a classical calculation. 

Even at 0 K, molecules do not stand still. Quantum mechanically, this unexpected behavior can be explained by the existence of a so-called zero-point energy. Therefore, simplifying a molecule by thinking of it as a collection of balls and springs which mediate the forces acting between the atoms is not totally unrealistic, because one can easily imagine how such a mechanical model wobbles aroimd, once activated by an initial force. Consequently, the movement of each atom influences the motion of every other atom within the molecule, resulting in a com-... 

Tlris is the Schrodinger equation for a simple harmonic oscillator. The energies of the system are given by E = (i + ) x liw and the zero-point energy is Hlj. 

Once the phonon frequencies are known it becomes possible to determine various thermodynamic quantities using statistical mechanics (see Appendix 6.1). Here again some slight modifications are required to the standard formulae. These modifications are usually a consequence of the need to sum over the points sampled in the Brillouin zone. For example, the zero-point energy is ... 

The second correction is much larger. The residual energy that the molecule ion has in the ground state above the T),- at the e(]nilibrintn bond length is the zero point energy. /PH. 

To obtain the G2 value of Eq we add five corrections to the starting energy, [MP4/6-31 lG(d,p)] and then add the zero point energy to obtain the ground-state energy from the energy at the bottom of the potential well. In Pople s notation these additive terms are... 

The second, third, and fourth corrections to [MPd/b-Jl lG(d,p)] are analogous to A (- -). The zero point energy has been discussed in detail (scale factor 0.8929 see Scott and Radom, 1996), leaving only HLC, called the higher level correction, a purely empirical correction added to make up for the practical necessity of basis set and Cl truncation. In effect, thermodynamic variables are calculated by methods described immediately below and HLC is adjusted to give the best fit to a selected group of experimental results presumed to be reliable. 

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