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Register a new userThe Theory of Uncertainty for Derived Results: Properties of Equations Representing Physicochemical Evaluation Systems
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B. P. Datta
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Any physiochemical variable (Ym) is always determined from certain measured variables {Xi}. The uncertainties {ui} of measuring {Xi} are generally a priori ensured as acceptable. However, there is no general method for assessing uncertainty (em) in the desired Ym, i.e. irrespective of whatever might be its system-specific-relationship (SSR) with {Xi}, and/ or be the causes of {ui}. We here therefore study the behaviors of different typical SSRs. The study shows that any SSR is characterized by a set of parameters, which govern em. That is, em is shown to represent a net SSR-driven (purely systematic) change in ui(s); and it cannot vary for whether ui(s) be caused by either or both statistical and systematic reasons. We thus present the general relationship of em with ui(s), and discuss how it can be used to predict a priori the requirements for an evaluated Ym to be representative, and hence to set the guidelines for designing experiments and also really appropriate evaluation models. Say: Y_m= f_m ({X_i}_(i=1)^N), then, although: e_m= g_m ({u_i}_(i=1)^N), N is not a key factor in governing em. However, simply for varying fm, the em is demonstrated to be either equaling a ui, or >ui, or even <ui. Further, the limiting error (d_m^(Lim.)) in determining an Ym is also shown to be decided by fm (SSR). Thus, all SSRs are classified into two groups: (I) the SSRs that can never lead d_m^(Lim.) to be zero; and (II) the SSRs that enable d_m^(Lim.) to be zero. In fact, the theoretical-tool (SSR) is by pros and cons no different from any discrete experimental-means of a study, and has resemblance with chemical reactions as well.
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Evaluation of a variable Yd from certain measured variable(s) Xi(s), by making use of their system-specific-relationship (SSR), is generally referred as the indirect measurement. Naturally the SSR may stand for a simple data-translation process in a given case, but a set of equations, or even a cascade of different such processes, in some other case. Further, though the measurements are a priori ensured to be accurate, there is no definite method for examining whether the result obtained at the end of an SSR, specifically a cascade of SSRs, is really representative as the measured Xi-values. Of Course, it was recently shown that the uncertainty (ed) in the estimate (yd) of a specified Yd is given by a specified linear combination of corresponding measurement-uncertainties (uis). Here, further insight into this principle is provided by its application to the cases represented by cascade-SSRs. It is exemplified how the different stage-wise uncertainties (Ied, IIed, ... ed), that is to say the requirements for the evaluation to be successful, could even a priori be predicted. The theoretical tools (SSRs) have resemblance with the real world measuring devices (MDs), and hence are referred as also the data transformation scales (DTSs). However, non-uniform behavior appears to be the feature of the DTSs rather than of the MDs.
Despite of their success, the results of first-principles quantum mechanical calculations contain inherent numerical errors caused by various approximations. We propose here a neural-network algorithm to greatly reduce these inherent errors. As a demonstration, this combined quantum mechanical calculation and neural-network correction approach is applied to the evaluation of standard heat of formation $DelH$ and standard Gibbs energy of formation $DelG$ for 180 organic molecules at 298 K. A dramatic reduction of numerical errors is clearly shown with systematic deviations being eliminated. For examples, the root--mean--square deviation of the calculated $DelH$ ($DelG$) for the 180 molecules is reduced from 21.4 (22.3) kcal$cdotp$mol$^{-1}$ to 3.1 (3.3) kcal$cdotp$mol$^{-1}$ for B3LYP/6-311+G({it d,p}) and from 12.0 (12.9) kcal$cdotp$mol$^{-1}$ to 3.3 (3.4) kcal$cdotp$mol$^{-1}$ for B3LYP/6-311+G(3{it df},2{it p}) before and after the neural-network correction.
It has been previously shown that any measurement system specific relationship (SSR)/ mathematical-model Y_d = f_d ({X_m}) or so is bracketed with certain parameters which should prefix the achievable-accuracy/ uncertainty (e_d^Y) of a desired result y_d. Here we clarify how the element-specific-expressions of isotopic abundances and/ or atomic weight could be parametrically distinguished from one another, and the achievable accuracy be even a priori predicted. It is thus signified that, irrespective of whether the measurement-uncertainty (u_m) could be purely random by origin or not, e_d^Y should be a systematic parameter. Further, by property-governing-factors, any SSR should belong to either variable-independent (F.1) or -dependent (F.2) family of SSRs/ models. The SSRs here are shown to be the members of the F.2 family. That is, it is pointed out that, and explained why, the uncertainty (e) of determining an either isotopic abundance or atomic weight should vary, even for any given measurement-accuracy(s) u_m(s), as a function of the measurable-variable(s) X_m(s). However, the required computational-step has been shown to behave as an error-sink in the overall process of indirect measurement in question.
By using Poissons summation formula, we calculate periodic integrals over Gaussian basis functions by partitioning the lattice summations between the real and reciprocal space, where both sums converge exponentially fast with a large exponent. We demonstrate that the summation can be performed efficiently to calculate 2-center Gaussian integrals over various kernels including overlap, kinetic, and Coulomb. The summation in real space is performed using an efficient flavor of the McMurchie-Davidson Recurrence Relation (MDRR). The expressions for performing summation in the reciprocal space are also derived and implemented. The algorithm for reciprocal space summation allows us to reuse several terms and leads to significant improvement in efficiency when highly contracted basis functions with large exponents are used. We find that the resulting algorithm is only between a factor of 5 to 15 slower than that for molecular integrals, indicating the very small number of terms needed in both the real and reciprocal space summations. An outline of the algorithm for calculating 3-center Coulomb integrals is also provided.
In isotope ratio mass spectrometry (IRMS), any sample (S) measurement is performed as a relative-difference ((S/W)di) from a working-lab-reference (W), but the result is evaluated relative to a recommended-standard (D): (S/D)di. It is thus assumed that different source specific results ((S1/D)di, (S2/D)di) would represent their sources (S1, S2), and be accurately intercomparable. However, the assumption has never been checked. In this manuscript we carry out this task by considering a system as CO2+-IRMS. We present a model for a priori predicting output-uncertainty. Our study shows that scale-conversion, even with the aid of auxiliary-reference-standard(s) Ai(s), cannot make (S/D)di free from W; and the ((S/W)di,(A1/W)di,(A2/W)di) To (S/D)di conversion-formula normally used in the literature is invalid. Besides, the latter-relation has been worked out, which leads to e.g., fJ([(S/W)dJCO2pmp%],[(A1/W)dJCO2pmp%],[(A2/W)dJCO2pmp%]) = ((S/D)dJCO2pm4.5p%); whereas FJ([(S/W)dJCO2pmp%],[(A1/W)dJCO2pmp%]) = ((S/D)dJCO2pm1.2p%). That is, contrary to the general belief (Nature 1978, 271, 534), the scale-conversion by employing one than two Ai-standards should ensure (S/D)di to be more accurate. However, a more valuable finding is that the transformation of any d-estimate into its absolute value helps improve accuracy, or any reverse-process enhances uncertainty. Thus, equally accurate though the absolute-estimates of isotopic-CO2 and constituent-elemental-isotopic abundance-ratios could be, in contradistinction any differential-estimate is shown to be less accurate. Further, for S and D to be similar, any absolute estimate is shown to turn out nearly absolute accurate but any (S/D)d value as really absurd. That is, estimated source specific absolute values, rather than corresponding differential results, should really represent their sources, and/ or be closely intercomparable.
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