Experimental Geometry

Among the experiments which were reported, there were several pertaining to measurements of the C-J (Chapman-Jouguet) particle velocity and sound speed and one experiment concerned with an examination of the polytropic equation of state for reaction products of condensed explosives 

Standard Laboratory Procedures for Determining Sensitivity, Brisance and Stability of Explosives , PATR 3278 (Dec 1965) [Superseding PATR FRL-TR-25 (l )6l] Impact Test with Picatinny Arsenal Apparatus (pp 2-4 and Figs 1, 2, 3 4, pp 32-35) Impact Test with US Bureau of Mines Apparatus (pp 4-7 and Figs 5, 6 7, pp 

136-38) Modified Impact Tests for Liquid Explosives (7) Explosion Temperature Test (pp 7-8 and Fig 8, p 39) Decomposition Temperature Test (8) Sensitivity to Initiation by Sand Test (pp 9-11 and Figs 9 10, 

pp 40-43) Sensitivity to Initiation by the Modified Sand Test for Liquid Explosives (12-14) Electrostatic Sensitivity Test (pp 14-15 and Figs 13, 14, pp 44-45) Brisance by Sand Test (16) Modified Sand Test to Determine Brisance of Liquid Explosives (16) Determination of Initiating Efficiency by Sand Test (17) Stability by 75°C International Test (18) Stability by 82.2°C KI Test (19) 100°C Heat Test (19) Vacuum Stability Tests at 90, 100 Be 120°C (pp 19-22 and Figs 15, 16 17, pp 46-48) Surveillance Tests at 65.5, 80, 120 134.5 C (pp 22-25 and Fig 18, p 49) Taliani Test (pp 25-27 

80) Donna Price T.P. Liddiard, Jr, The Small Scale Gap Test Calibration and Comparison with the Large Scale Gap Test , NOLTR 66-87(1966), White Oak, Maryland [The SSGT, first described in 1952 by Dim-mock, Jr (Ref 26), has been used in its modified form, described in 1961 by Ayres (Ref 

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TabU 3-5 Dipole moments calculated for formaldehyde using various basis sets at the experimental geometry,... 

Fig. 3.57. Different experimental geometries for low energy ions spectroscopies.

An interesting point concerns polarisation effects in the Raman spectra, which are commonly observed in low-dimensional materials. Since CNTs are onedimensional (ID) materials, the use of light polarised parallel or perpendicular to the tube axis will give information about the low dimensionality of the CNTs. The availability of purified samples of aligned CNTs would allow us to obtain the symmetry of a mode directly from the measured Raman intensity by changing the experimental geometry, such as the polarisation of the light and the sample orientation, as discussed in this chapter. 

Once you have completed this first calculation, devise and run calculations which will determine the lowest energy electronic state for ozone. Use the experimental geometry 0-0 bond lengths=1.272 A, 0-0-0 bond angle=116.8 . 

All of the predicted structures are at least reasonably good. The two hybrid functionals produce the best structures, in excellent agreement with the experimental geometry. The SVWN and SVWNS functionals both produce good structures, while the BLYP geometry is the least accurate. 

You ll need to run five calculations at each model chemistry oxygen atom, chlorine atom, O2, CIO and ozone (but don t forget that you can obtain lower-level energies from a higher-level calculation). Use the experimental geometries for the various molecules and the following scaled zero-point energy corrections ... 

Here is a KS-LCAO calculation on water at the experimental geometry of 95.7pm and 104.5°. I chose the BLYP functional this comprises Becke s 1988... 

The experimental geometry for H2O has a bond length of 0.9578 A and an angle of 104.48°. Let us investigate how the calculated geometry change as a function of theoretical sophistication. 

The calculated ioi as a function of basis set and electron correlation (valence electrons only) at the experimental geometry is given in Table 11.8. As the cc-pVXZ basis sets are fairly systematic in how they are extended from one level to the next, there is some justification for extrapolating the results to the infinite basis set limit (Section 5.4.5). The HF energy is expected to have an exponential behaviour, and a functional form of the type A + 5exp(—Cn) with n = 2-6 yields an infinite basis set limit of —76.0676 a.u., in perfect agreement with the estimated HF limit of -76.0676 0.0002 a.u. ... 

Table 10 and Figure 17 carry all the necessary information. Since the only experimental geometry available is that for the sulphoxide, the ring geometry was kept constant in all three compounds, while OCS and OSO angles and S—O distances were taken from the analogous dimethyl derivatives. 

TABLE 3. Experimental geometries of selected acyclic and three-membered sulfones and sulfoxides (16-19)... 

And finally, we may mention that a statistical analysis of the sulfur d orbital problem has been carried out with dimethyl sulfoxide as a model compound36. The results provide a clear answer to the sulfur d orbital problem, since no simultaneous reproduction of experimental geometry and an adequate approximation to the variationally optimum total energy have been possible without including d polarization functions on sulfur . 

Table 1 Coefficients for 7[ (a ) for third harmonic generation (THG), degenerate four wave mixing (DFWM), electric field induced second harmonic generation (ESHG), and Kerr effect in methane at the experimental geometry rcH = 2.052 a.u. A CCSD wavefunction and the t-aug-cc-pVDZ basis were used. (Results given in atomic units, the number in parentheses indicate powers of ten.)...

In CDAD, a chiral experimental geometry is created about a fixed molecular orientation, and the asymmetry in the electron distribution can be observed in directions mutually perpendicular to the photon propagation direction and the... 

The second row in Fig. 15 shows examples at the three selected photon energies of the C=0 15 difference spectra obtained for both enantiomers. After normalization by the mean spectrum the asymmetry factor F(54.7°) is plotted along the bottom row. After correction for the cos(54.7°) term arising from the specific experimental geometry the net forward-backward asymmetry, y, can be estimated to reach a peak 15% in the hv = 298.7-eV photoionization. 

The symmetry assignment of vibrational states refers to C3V point group. Experimental geometries and wave numbers are taken from [28,29] for CH3 and [30] for CF3. EPR parameters are taken from [31] forCH3 at %K and [32] forCF3..at77K. 

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