Y123.EXE and OPT123.EXE - supplementary software for the paper "Simultaneous assessment of the YBa2Cu3O6+z thermodynamics under the linear error model" by E.B. Rudnyi, V.V. Kuzmenko, and G.F. Voronin presented at Forth Electronic Computational Chemistry Conference, http://hackberry.chem.niu.edu/ECCC4/, November 1997. E.B. Rudnyi Department of Chemistry Moscow State University 119899 Moscow, Russia e-mail RUDNYI@COMP.CHEM.MSU.SU http://www.chem.msu.su/~rudnyi/welcome.html (C) 1997, All rights reserved Requirements: A computer with Windows 95 or Windows NT. You are supposed to be familiar with Command Prompt because both programs are working from the command line only. Sorry for inconvenience. Files Y123.EXE program to compute thermodynamics properties of the Y123 phase OPT123.EXE program to estimate unknown parameters in the Gibbs energy of Y123 phase from experimental values ALL.DAT database of experimental values for the Y123 phase ML.SET hypotheses for solution ML WLS.SET hypotheses for solution WLS ML.MOD Gibbs energy of Y123 for solution ML FIX.MOD Gibbs energy of Y123 for the solution obtained by 93DEG/VOR WLS.MOD Gibbs energy of Y123 for solution WLS Y123.MOD the same as ML.MOD. This file is required for both Y123 and OPT123 FIX.LST OPT123 listing for the solution obtained by 93DEG/VOR ML.LST OPT123 listing for solution ML WLS.LST OPT123 listing for solution WLS README.TXT this file LICENSE This program is freeware (public domain). Feel free to use and distribute it, provided no charge is taken. Let me know if you find any bug. I would also appreciate your comments. Disclaimer of warranty: This program is supplied as is. I disclaim all warranties, express or implied, including, without limitation, the warranties of merchantability and of fitness of this program for any purpose. I assume no liability for damages direct or consequential, which may result from the use of this program. 1. Y123.EXE This program computes thermodynamics properties of the Y123 phase x - the order parameter Cpz - heat capacity in J/K/mol S - entropy in J/K/mol H - H298 - change in enthalpy in kJ/mol Del_ox_H - enthalpy of formation from oxides (Eq. 3 in the paper) ln{pO2/po} - oxygen partial pressure over Y123 based on the parameters of the Gibbs energy taken from file Y123.MOD. From the start this file contains the values for our recommended solution, ML, however you can rewrite it. For example copy FIX.MOD Y123.MOD After this Y123 will compute thermodynamic properties for the solution obtained by 93DEG/VOR. Thus, while computing thermodynamic properties pay attention to what is written in file Y123.MOD. The program can compute the thermodynamic properties of the Y123 phase either at constant index z Y123 -T z_value T_min T_max T_step or at constant T Y123 -z T_value z_min z_max z_step For example, the next command Y123 -T .5 300 1300 100 will produce thermodynamic properties for the composition with z = 0.5 from 300 K to 1300 K. 2. OPT123.EXE This program is much more complicated than Y123.EXE. It was the main computational engine in our project. OPT123.EXE takes file Y123.MOD as the description of the model and also as the source for the initial values of unknown parameters. Then it reads two files, a file with experimental values (data_file) and a file with expert hypotheses (expert_file), maximizes the likelihood function and writes the output to the listing. The basic format of the command is OPT123 data_file[.dat] expert_file[.set] There are some options, the list of options can be produced by the command without parameters OPT123 For example, after the command OPT123 all ml -otest the model will be read from Y123.MOD, the experimental values are from ALL.DAT, the hypotheses are from ML.SET. The results will be written to file TEST.LST. Without the option -o, the results would be written to file ML.LST and as the result they would overwrite file ML.LST supplied by me. The results, file TEST.LST, should be quite close to my file ML.LST. If this is not the case, then something went wrong. Command OPT123 all wls -otest2 should produce listing that should be close to my WLS.LST. So, what you can do with OPT123. First, you can add new experimental values to file ALL.DAT and see what happens. If you do have new experimental values for the Y123 phase, please also let me know. I would appreciate this. Note that after adding new experimental values to ALL.DAT, some modification should be made to the file with hypotheses, otherwise you may receive useless results. Second, you can change the hypotheses and obtain new values of parameters under your own hypotheses. To this end, you have got to write you own expert_file (you can take as a background either ML.SET or WLS.SET). However, before this I would recommend you to read the paper first. 2.1. Format of data_file This file is written in the free format. White space is recognized as the word delimiter. The file consists from experiments separated by semicolon. Each experiment comprises following fields separated by commas experiment_ID, equation_ID, variables_names, point1, point2, ...; experiment_ID - this is any identifier (list of symbols without space, comma or semicolon). equation_ID - predefined identifier (see ALL.DAT for what can be written here) variables_names - two or more identifiers separated by space. Their quantity determines the total number of values in each point. The identifiers themselves are not employed by the program. point1 - two or more values separated by space. The number of values to read is equal to the number of names of variables. If there are a few words in the fields experiment_ID or equation_ID, the first only is taken and all the others are ignored. If there are more values in the field pointN than the number of the names of variables, the extra values are ignored. If the number of values is less than that, absent are initialized by zeros. Such rules permit you to write comments in the fields experiment_ID, equation_ID and pointN. You can exclude either an experiment or a point from processing. To exclude a series - put symbol * before the name of the experiment, to exclude a point - put symbol * in the beginning of the field pointN. You also can exclude an experiment in expert_file. 2.2. Format of expert_file If expert_file is absent, OPT123 LINEAR makes calculation with default hypotheses - all the series are assumed to have the same reproducibility variances sr_i2 = sr_2 and the same quantities ga_i = ga and gb_i = gb. In the case of Y123 it is completely useless. Expert_file is written in the free format and contains the descriptions of the experiments and the description START. These descriptions must be finished by semicolon. OPT123 reads an experiment description, modifies the hypotheses accordingly and continues reading the next description. When the description START appears, the utility starts the calculation. The format of an experiment description is [*] experiment_ID, hyp_fl sri, hyp_fl sga, hyp_fl sgb; * - this symbol, if present, means that the experiment will be ignored. experiment_ID - the name of the experiment. All the words after the first will be ignored until comma. hyp_fl - the hypothesis flag - one of three characters #, % or *. See below. sri - the initial value of the standard deviation of reproducibility. sga - the initial value of sqrt(ga_i). sgb - the initial value of sqrt(gb_i). Character % shows that this variance component will be assumed as an individual unknown. Character * makes the variance component constant - it won't be changed in the maximization procedure. Character # means that the values of this variance component should be the same as in the like group shown by subsequent number (0 <= i <= 19). The groups for sri, sga and sgb are assumed to be different. For example, next lines ex1, #2 1, % 0 , * 1; ex2, #2 1, #3 0.5, #3 0; ex3, #4 2, #3 0.5, #3 0; ex4, #4 2, #3 0.5, % 0; describe that we have 6 unknown variance components 1) sr1 = sr2 2) sr3 = sr4 3) sga1 4) sga2 = sga3 = sga4 5) sgb2 = sgb3 6) sgb4 sgb1 is assumed to be constant. 2.3. Listing Listing is self-descriptive. If you have any question, please contact me.