Quantum Mechanical Foundations of Molecular Spectroscopy. Max Diem. Читать онлайн. Newlib. NEWLIB.NET

Автор: Max Diem
Издательство: John Wiley & Sons Limited
Серия:
Жанр произведения: Химия
Год издания: 0
isbn: 9783527829606
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p equals h slash normal lamda

      For photons, the wave properties are manifested by diffraction experiments and summarized by Maxwell's equation. As for all wave propagation, the velocity of light, c, is related to wavelength λ and frequency ν by

      with c = 2.998 × 108 [m/s] and λ expressed in [m] and ν expressed in [Hz = s−1]. The quantity normal nu overTilde is referred to as the wavenumber of radiation (in units of m−1 or cm−1) that indicates how many wave cycles occur per unit length:

      The (kinetic) energy of a photon is given by

      (1.13)upper E equals h normal nu equals italic h c slash normal lamda equals normal h with stroke omega

      with ħ = h/2π and ω, the angular frequency, defined before as ω = 2πν.

      (1.14)p equals m normal v or p equals italic m c

      it follows that the photon mass is given by

      Notice that a photon can only move at the velocity of light and the photon mass can only be defined at the velocity c. Therefore, a photon has zero rest mass, m0.

      Particles of matter, on the other hand, have a nonzero rest mass, commonly referred to as their mass. This mass, however, is a function of velocity v and should be referred to as mν, which is given by

      Example 1.1 Calculation of the mass of an electron moving at 99.0 % of the velocity of light (such velocities can easily be reached in a synchrotron).

      Answer:

      (E1.1.1)StartLayout 1st Row 1st Column m Subscript normal v 2nd Column equals StartFraction 9.109 times 10 Superscript negative 31 Baseline Over StartRoot 1 minus left-parenthesis StartFraction 0.99 normal c squared Over c squared EndFraction right-parenthesis EndRoot EndFraction equals StartFraction 9.109 times 10 Superscript negative 31 Baseline Over StartRoot 1 minus left-parenthesis 0.990 right-parenthesis squared EndRoot EndFraction equals StartFraction 9.109 times 10 Superscript negative 31 Baseline Over StartRoot 0.0199 EndRoot EndFraction equals StartFraction 9.109 times 10 Superscript negative 31 Baseline Over 0.141 EndFraction 2nd Row 1st Column Blank 2nd Column equals 6.457 times 10 Superscript negative 30 Baseline left-bracket k g right-bracket EndLayout

      The electron at 99 % of the velocity of light has a mass of about seven times its rest mass.

      Equation (1.16) demonstrates that the mass of any matter particle will reach infinity when accelerated to the velocity of light. Their kinetic energy at velocity ν (far from the velocity of light) is given by the classical expression

      (1.17)upper E Subscript k i n Baseline equals one half italic m v squared equals p squared slash 2 m

      The discussion of the last paragraphs demonstrates that at the beginning of the twentieth century, experimental evidence was amassed that pointed to the necessity to redefine some aspects of classical physics. The next of these experiments that led to the formulation of quantum mechanics was the observation of “spectral lines” in the absorption and emission spectra of the hydrogen atom.

Schematic illustration of the portion of the hydrogen atom emission in the visible spectral range, represented as a line spectrum and schematically as an emission spectrum.

      These experiments demonstrated that the H atom can exist in certain “energy states” or “stationary states.” These states can undergo a process that is referred to as a “transition.” When the atom undergoes such a transition from a higher or more excited state to a lower or less excited state, the energy difference between the states is emitted as a photon with an energy corresponding to the energy difference between the states: