By Magdolna Hargittai, Istvan Hargittai
ISBN-10: 0080545904
ISBN-13: 9780080545905
ISBN-10: 0762302089
ISBN-13: 9780762302086
Read or Download Advances in Molecular Structure Research, Volume 3, First Edition (Advances in Molecular Structure Research) PDF
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Extra info for Advances in Molecular Structure Research, Volume 3, First Edition (Advances in Molecular Structure Research)
Sample text
Tin uA 2. din h. ~orrected ab initio data. fThe diagnostics are in boldface when significant. the three experimental equilibrium moments of inertia gives a condition number K: = 104 and indicates that the two distances are fully correlated. This explains why the result is not reliable: small errors of the rotational constants are magnified by the large condition number. If we add a fourth experimental moment of inertia, that of DCO +, the condition number drops to 7 which is good, but the outlier diagnostics indicate that this fourth datum is not compatible with the other three and is an influential point (see Table 12).
In fact, in DCO +, the state 0111 is nearly degenerate with 10~ and the resulting large anharmonic interaction leads to a much too small vibration-rotation interaction constant Ctl. As a result, adding the experimental Ie(DCO +) does not lead to better results although it improves the conditioning. One remedy of the problem is to estimate the equilibrium rotational constants by correcting the experimental ground state rotational constants with the a b initio Bo - Be as done by Puzzarini et al. C).
E. e. the structural parameters to be determined. The GaussNewton method of successive iterations allows nonetheless the application of the popular linear least-squares procedure. For this purpose the problem is linearized by an expansion in the neighborhood of the expected solution. For each iteration, the observations are the differences between the inertial moments of the original input and the approximations computed from the present structure, while the solutions produce corrective increments to this structure.
Advances in Molecular Structure Research, Volume 3, First Edition (Advances in Molecular Structure Research) by Magdolna Hargittai, Istvan Hargittai
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