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Figure 2.1-1 Models of a harmonic oscillator, a mass m on a spring with the force constantf, b two masses, rnl and rn2, connected by a spring

10 2

The following formula, in cell G3, calculates the value for c:

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system In order to minimize cryopumping vapors (water, oil, etc), a 77 K radiation shield surrounding the matrix support is strongly recommended A matrix is a nonequilibrium solution of trapped species in a solid noble gas In order to minimize the chances of aggregation among the trapped species, the heat of condensation of the matrix gas must be transferred as fast as possible to the refrigerant, and the mobile layer between the solid matrix and the gas phase must be very small Thus, the matrix support is usually connected to the refrigerator using indium foil as a very efficient thermal conductor However, the cold surface may, if it is not entirely clean, offer some resistance to the heat transfer Furthermore, the thermal conductivity of a solid noble gas is considerably temperature dependent; eg, argon shows maximum conductivity at 10 K.

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At this temperature, an argon matrix should therefore be formed by continuous deposition The deposition rate (05-5 mmol argon h ) is dependent on the geometry of the matrix assembly (spray-on nozzle, matrix support, distance to pump) and on the concentration, size, and intermolecular forces of the matrix-isolated species The optimum conditions for minimizing aggregation and obtaining a transparent matrix can be found only by trial and error If the temperature of the matrix support and the cooling power of the refrigerator are insufficient, aggregation problems can be overcome by applying the pulsed deposition technique (Perutz and Turner, 1973) For cooling, a great variety of closed-cycle refrigerators and continuous-flow helium cryostats are commercially available Closed-cycle refrigerators based on the Sterling principle (Gifford and McMahon, 1960) operate at about 10-12 K, with enough cooling power for most matrix applications.

In addition, three-stage closed-cycle refrigeration systems capable of 1 W at 42 K are available for neon matrix experiments These devices combine a two-stage closed cycle cooler with a Joule-Thompson expansion cycle The advantages of a continuous-flow helium cryostat are apparent only where higher cooling power and faster cooling downfwarming up cycles are desired Even under optimal conditions of matrix deposition, yielding exclusively monomeric species of interest in a transparent matrix, distinct absorptions in the infrared spectrum often appear as multiplets spread over a few wavenumbers This complicates the interpretation of matrix spectra and is known as the matrix effect The matrix effect is due to the fact that isolated particles occupy different substitutional lattice sites (which differ slightly in energy).

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