A U.S. Department of EnergyOffice of Science LaboratoryOperated by The University of Chicago
* Argonne National Laboratory, Argonne, IL
Office of ScienceU.S. DEPARTMENT OF ENERGY
Active Thermochemical Tables: Thermochemistry for the 21st Century
Branko Ruscic*,R. E Pinzon*, G. von Laszewski*, D. Kodeboyina*,
A. Burcat* (Technion), D. Leahy (SNL), D. Montoya (LANL), and A. F. Wagner*
16 1718 19
H2O → OH+ + H + e-
15 H2O → OH + H
20 2122 22a
OH → OH+ + e-
3 4 OH → O + H
14
H2O2 → 2 OH
5 6
H2O (l) → H2O
10 11 12
H2O2 (l) → H2O2
23
½ H2 + ½ O2 → OH
2
H2 → 2 H
7 8 9
H2 + ½ O2 → H2O (l)
13
H2O2 (l) → H2O (l) + ½ O2
1
O2 → 2 O
O2
OH+ OH
H2O
H2O (l)
H2
H2O2 (l)
H2O2
OH
THANKS TOTHANKS TO……• Supported by the
U.S. Department of EnergyU.S. Department of Energy
•• Numerous collaboratorsNumerous collaborators:•• CMCS TeamCMCS Team
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
Division of Chemical Sciences, Geosciences and Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy SciencesBiosciences, Office of Basic Energy Sciences,and Division of Mathematical, Information and Computational SciencesDivision of Mathematical, Information and Computational Sciences, , Office of Advanced Scientific Computing ResearchOffice of Advanced Scientific Computing Research
CMCS
• Melita L. Morton (ANL/postddoc), Sandra J. Bittner (ANL), Sandeep G. Nijsure (ANL), Michael Minkoff (ANL), Lawrence B. Harding (ANL), Joe V. Michael (ANL), Stephen Gray (ANL), John Stanton (UT Austin), Attila Csaszar (ELTE Budapest), Mihaly Kallay (U. Mainz), Tamas Turanyi (ELTE Budapest), David A. Dixon (U. Ala.), David Feller (PNNL), Kirk Peterson (PNNL/WSU), David Schwenke (NASA Ames), Cheuk-Yiu Ng (UC Davis)…
•• IUPAC Task Group for Thermochemistry of RadicalsIUPAC Task Group for Thermochemistry of Radicals
WHAT ARE WHAT ARE ACTIVE THERMOCHEMICAL TABLES?ACTIVE THERMOCHEMICAL TABLES?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
WHAT ARE WHAT ARE ACTIVE THERMOCHEMICAL TABLES?ACTIVE THERMOCHEMICAL TABLES?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
Active Thermochemical Tables (ATcT):Active Thermochemical Tables (ATcT):a novel scientific application, centered on a distinctively different paradigm of how to derive accurate, reliable, and internally consistent accurate, reliable, and internally consistent thermochemical valuesthermochemical values
thermochemistry as it befits the 21st centuryrapidly becoming the archetypal approach (ATcT are appearing as a new encyclopedic term in the 2005 Yearbook of Science and Technology, an annual update to theMcGraw-Hill Encyclopedia of Science and Technology)
first implementation of the broader idea of Active TablesActive Tables
WHAT IS THE GENERAL WHAT IS THE GENERAL IDEA BEHIND ACTIVE TABLES?IDEA BEHIND ACTIVE TABLES?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
Many databases store and display data items that:are not directly measurable observablesnot directly measurable observables, andare interdependentinterdependent in a non-transparent way,
because they arederivedderived in a (usually) complex way from more basic determinationsmore basic determinations
In most cases, these databases do not expose or even storedo not expose or even store either
the basic determinations, or the data interdependencies
Dear consequence:the database cannot be easily updated when new information becomes available and hence becomes obsolete
The idea behind Active TablesActive Tables is not to store derived data, but rather the basic determinations and the dependenciesthe basic determinations and the dependencies, and update the derived data as frequently as neededupdate the derived data as frequently as needed
WHAT DO WE NEED GOOD WHAT DO WE NEED GOOD THERMOCHEMISTRY FOR?THERMOCHEMISTRY FOR?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
Knowledge of thermochemical stability of chemical species is central to chemistry and essential in many industriesAccurate, reliable, and self-consistent thermochemistry is
a conditio sine qua non in chemical kinetics, construction of reaction mechanisms, formulation of multi-scale chemical models that have predictive abilities, etc.historically the strongest spiritus movens for the development and improvement of electronic structure theoriesa stimulating environment fostering abstraction of generalities leading to new insights into details of chemical bonding
Availability of well-defined and properly quantified uncertainties is becoming increasingly important as the fidelity levels of electronic structure theory and computer modeling of complex chemical environments are increasing
THERMOCHEMICALTHERMOCHEMICALTABLESTABLES
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
Tabulations of thermochemical properties, conveniently sorted by chemical species Tabulated thermochemical properties are derived from other, more direct determinations
SpeciesSpecies--interrelatinginterrelating determinations (D0, ∆∆rrHH°°TT, , KK°°eqTeqT, electrode potentials, electrode potentials, solubsolub. . constconst’’ss, etc), etc)∆∆ffHH°° and/or and/or ∆∆ffGG°° at one temperatureat one temperature
SpeciesSpecies--specificspecific determinations (lists of levels, spectroscopic constants, direct measurements of Cp , etc), etc)partitionpartition--function Qfunction QTT related thermochemical inforelated thermochemical info:
[H[H°°TT--HH°°00]/RT]/RT = T ∂(ln QT)/∂T = <E>/kT = ∫ C°pT/R dTSS°°TT/R/R = T ∂(ln QT)/∂T + ln QT = <E>/kT + ln QT = ∫ C°pT/R/T dTΦΦ°°TT/R/R = ln QT = S°T/R - [H°T-H°0]/RTCC°°pTpT/R/R = T2 ∂2(ln QT)/∂T2 + 2 T ∂(ln QT)/∂T = <E2>/(kT)2 - (<E>/kT)2
and TT--dependencedependence of ∆∆ffHH°° and ∆∆ffGG°°
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
selected ∆Hf° at areference T (0 or 298 K)
discussion & background info with partial species-interrelating info
T-dependent functions: Cp°, S°, (H°T – H0°), ∆Hf°, …
some species-specificinfo
TRADITIONAL TRADITIONAL SEQUENTIAL THERMOCHEMISTRYSEQUENTIAL THERMOCHEMISTRY
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
The nature of the inexorable speciesspecies--interrelating determinationsinterrelating determinationscauses considerable complications…Traditional approach: sequential thermochemistrysequential thermochemistry
one target speciesone target species per stepavailable speciesspecies--interrelatinginterrelating information relating the target species to those previously determinedto those previously determined is examinedthe the ““bestbest”” determination is selected manuallyand used to derive ∆∆ffHH°° at one Tat one Tavailable available speciesspecies--specificspecific info is used to derive info is used to derive TT--dependence and other functionsdependence and other functionsthermochemistry for the target species isthermochemistry for the target species is frozenfrozenand used as a constant in subsequent stepsand used as a constant in subsequent stepssequence follows the sequence follows the ““standard order of the elementsstandard order of the elements””
DEFICIENCIES OF THE DEFICIENCIES OF THE TRADITIONAL APPROACHTRADITIONAL APPROACH
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
Traditional thermochemical tables have a maze of hiddenhidden progenitor-progeny relationships
Consequently, traditional tables are next to impossible to properly updateimpossible to properly update with new knowledge
New determinations can be used, at best, to “improve” things locallylocally, for one target speciesThis immediately introduces newnew inconsistenciesinconsistencies across the table, since there will be other species pegged to the old value of the newly revised species; it is not explicit which those may be
The “adopt and freeze” sequential approachcreates a hiddenhidden cumulative errorcumulative error(lack of feedback to frozen values)produces uncertainties that do notdo not properlyproperly reflectreflect all the knowledgethat was available (e.g. knowledge used only during later steps, or wasdiscarded because it lagged behind the selected “best” determination) (BTW, uncertainties are the NBT)
Available knowledge is used only partiallyonly partially, at best
THE APPROACH OF THE APPROACH OF ACTIVE THERMOCHEMICAL TABLESACTIVE THERMOCHEMICAL TABLES
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
As opposed to As opposed to conventional sequential thermochemistry, , Active Thermochemical TablesActive Thermochemical Tablesare based on the are based on the Thermochemical Network approachThermochemical Network approach, , hence:hence:
addressing and correcting the mentioned deficienciesaddressing and correcting the mentioned deficienciesof traditional tables, and, at the same timeof traditional tables, and, at the same timeintroducing a number ofintroducing a number of completely new featurescompletely new features(such as: (such as: rapid update with new informationrapid update with new information,,““what ifwhat if”” tests, tests, ““weakest linkweakest link”” isolation, availability of isolation, availability of the the full covariance matrixfull covariance matrix, the , the sensitivity matrixsensitivity matrix, etc.), etc.)
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
CH
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)CH
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
H2
D0(H2)
CH
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
H2
D0(H2)
CH
D0(CO) CO
O
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
H2
D0(H2)
CH
D0(CO) CO
O2
D0(O2)
O
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
H2
D0(H2)
CH
D0(CO) CO
CO + 1/2O2 → CO2
CO2
O2
D0(O2)
O
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
H2
D0(H2)
CH
D0(CO) CO
CO + 1/2O2 → CO2
C(grph) + CO2 → 2CO
CO2
O2
D0(O2)
O
C(grph)
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
H2
D0(H2)
CH
D0(CO) CO
CO + 1/2O2 → CO2
C(grph) + CO2 → 2CO
CO + H2O → CO2 + H2H2O
CO2
O2
D0(O2)
O
C(grph)
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
H2
D0(H2)
CH
D0(CO) CO
CO + 1/2O2 → CO2
C(grph) + CO2 → 2CO
CO + H2O → CO2 + H2C(grph) + O2 → CO2 H2O
CO2
O2
D0(O2)
O
C(grph)
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
∆vapH(H2O)
H2
D0(H2)
CH
D0(CO) CO
CO + 1/2O2 → CO2
C(grph) + CO2 → 2CO
CO + H2O → CO2 + H2C(grph) + O2 → CO2
H2O(l)
H2O
CO2
O2
D0(O2)
O
C(grph)
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
∆vapH(H2O)
H2
D0(H2)
CH
D0(CO) CO
CO + 1/2O2 → CO2
C(grph) + CO2 → 2CO
CO + H2O → CO2 + H2C(grph) + O2 → CO2
H2 + 1/2O2 → H2O(l)H2O(l)
H2O
CO2
O2
D0(O2)
O
C(grph)
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
∆vapH(H2O)
H2
D0(H2)
CH
D0(CO) CO
CO + 1/2O2 → CO2
C(grph) + CO2 → 2CO
CO + H2O → CO2 + H2C(grph) + O2 → CO2
H2 + 1/2O2 → H2O(l)H2O(l)
H2O
CO2
O2
D0(O2)
O
C(grph)
∆sublH(C(grph))
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
∆vapH(H2O)
H2
D0(H2)
CH
D0(CO) CO
CO + 1/2O2 → CO2
C(grph) + CO2 → 2CO
CO + H2O → CO2 + H2C(grph) + O2 → CO2
H2 + 1/2O2 → H2O(l)H2O(l)
H2O
CO2
O2
D0(O2)
O
C(grph)
∆sublH(C(grph))
•• Primary verticesPrimary vertices: sought-for enthalpies of formation
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
∆vapH(H2O)
H2
D0(H2)
CH
D0(CO) CO
CO + 1/2O2 → CO2
C(grph) + CO2 → 2CO
CO + H2O → CO2 + H2C(grph) + O2 → CO2
H2 + 1/2O2 → H2O(l)H2O(l)
H2O
CO2
O2
D0(O2)
O
C(grph)
∆sublH(C(grph))
•• Secondary verticesSecondary vertices: experimentally/theoretically accessible quantities (∆Hr°, ∆Gr°, Keq,…)
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
∆vapH(H2O)
H2
D0(H2)
CH
D0(CO) CO
CO + 1/2O2 → CO2
C(grph) + CO2 → 2CO
CO + H2O → CO2 + H2C(grph) + O2 → CO2
H2 + 1/2O2 → H2O(l)H2O(l)
H2O
CO2
O2
D0(O2)
O
C(grph)
∆sublH(C(grph))
•• Edges (directed and weighted)Edges (directed and weighted): participation in chemical reactions
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
∆vapH(H2O)
H2
D0(H2)
CH
D0(CO) CO
CO + 1/2O2 → CO2
C(grph) + CO2 → 2CO
CO + H2O → CO2 + H2C(grph) + O2 → CO2
H2 + 1/2O2 → H2O(l)H2O(l)
H2O
CO2
O2
D0(O2)
O
C(grph)
∆sublH(C(grph))
•• Secondary vertices may have Secondary vertices may have multiple degeneraciesmultiple degeneracies(competing measurements) ::
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
∆vapH(H2O)
H2
D0(H2)
CH
D0(CO) CO
CO + 1/2O2 → CO2
C(grph) + CO2 → 2CO
CO + H2O → CO2 + H2C(grph) + O2 → CO2
H2 + 1/2O2 → H2O(l)H2O(l)
H2O
CO2
O2
D0(O2)
O
C(grph)
∆sublH(C(grph))
•• Generally there will be a Generally there will be a significant number of significant number of alternativealternative paths between paths between primary verticesprimary vertices
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
CF3I
CF3Cl
10
16, 21, 25, 27
9
11, -12
18
6 13, 14, 15, 17, 28
CF3Br CF3 22, 23, 24, 26
8
7
19 C2F6 CF3CNCF3H C2F4
420 5 1,2,3
•• Generally there will be Generally there will be a significant number of a significant number of alternativealternative paths between paths between primary verticesprimary vertices
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
CF3I
CF3Cl
10
16, 21, 25, 27
9
11, -12
18
6 13, 14, 15, 17, 28
CF3Br CF3 22, 23, 24, 26
8
7
19 C2F6 CF3CNCF3H C2F4
420 5 1,2,3
•• Generally there will be Generally there will be a significant number of a significant number of alternativealternative paths between paths between primary verticesprimary vertices
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
CF3I
CF3Cl
10
16, 21, 25, 27
9
11, -12
18
6 13, 14, 15, 17, 28
CF3Br CF3 22, 23, 24, 26
8
7
19 C2F6 CF3CNCF3H C2F4
420 5 1,2,3
•• Generally there will be Generally there will be a significant number of a significant number of alternativealternative paths between paths between primary verticesprimary vertices
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
CF3I
CF3Cl
10
16, 21, 25, 27
9
11, -12
18
6 13, 14, 15, 17, 28
CF3Br CF3 22, 23, 24, 26
8
7
19 C2F6 CF3CNCF3H C2F4
420 5 1,2,3
•• Generally there will be Generally there will be a significant number of a significant number of alternativealternative paths between paths between primary verticesprimary vertices
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
CF3I
CF3Cl
10
16, 21, 25, 27
9
11, -12
18
6 13, 14, 15, 17, 28
CF3Br CF3 22, 23, 24, 26
8
7
19 C2F6 CF3CNCF3H C2F4
420 5 1,2,3
•• Generally there will be Generally there will be a significant number of a significant number of alternativealternative paths between paths between primary verticesprimary vertices
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
CF3I
CF3Cl
10
16, 21, 25, 27
9
11, -12
18
6 13, 14, 15, 17, 28
CF3Br CF3 22, 23, 24, 26
8
7
19 C2F6 CF3CNCF3H C2F4
420 5 1,2,3
•• Generally there will be Generally there will be a significant number of a significant number of alternativealternative paths between paths between primary verticesprimary vertices
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
WHAT IS AWHAT IS ATHERMOCHEMICAL NETWORK ?THERMOCHEMICAL NETWORK ?
CF3I
CF3Cl
10
16, 21, 25, 27
9
11, -12
18
6 13, 14, 15, 17, 28
CF3Br CF3 22, 23, 24, 26
8
7
19 C2F6 CF3CNCF3H C2F4
420 5 1,2,3
•• Generally there will be Generally there will be a significant number of a significant number of alternativealternative paths between paths between primary verticesprimary vertices
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
• The best setbest set of ∆Hf°s describing allallunderlying knowledge is obtained NOT by choosing a particular NOT by choosing a particular sequential path through the TNsequential path through the TN, but by simultaneous solutionsimultaneous solution of thenetwork (via minimization of a suitable statistic, such as χ2),preceded preceded by a a statistical analysisstatistical analysis of TN (to isolate “optimistic” uncertainties)
SOLVING THESOLVING THETHERMOCHEMICAL NETWORKTHERMOCHEMICAL NETWORK
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
∆vapH(H2O)
H2
D0(H2)
CH
D0(CO) CO
CO + 1/2O2 → CO2
C(grph) + CO2 → 2CO
CO + H2O → CO2 + H2C(grph) + O2 → CO2
H2 + 1/2O2 → H2O(l)H2O(l)
H2O
CO2
O2
D0(O2)
O
C(grph)
∆sublH(C(grph))
•• TN preconditioningTN preconditioningis very important:is very important:““optimisticoptimistic”” uncertainties uncertainties will skew the resultwill skew the result
SOLVING THESOLVING THETHERMOCHEMICAL NETWORKTHERMOCHEMICAL NETWORK
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
∆vapH(H2O)
H2
D0(H2)
CH
D0(CO) CO
CO + 1/2O2 → CO2
C(grph) + CO2 → 2CO
CO + H2O → CO2 + H2C(grph) + O2 → CO2
H2 + 1/2O2 → H2O(l)H2O(l)
H2O
CO2
O2
D0(O2)
O
C(grph)
∆sublH(C(grph))
•• TN preconditioningTN preconditioning::redundant loops checkredundant loops check
SOLVING THE SOLVING THE THERMOCHEMICAL NETWORKTHERMOCHEMICAL NETWORK
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
∆vapH(H2O)
H2
D0(H2)
CH
D0(CO) CO
CO + 1/2O2 → CO2
C(grph) + CO2 → 2CO
CO + H2O → CO2 + H2C(grph) + O2 → CO2
H2 + 1/2O2 → H2O(l)H2O(l)
H2O
CO2
O2
D0(O2)
O
C(grph)
∆sublH(C(grph))
•• TN preconditioningTN preconditioning::““worst offenderworst offender”” strategystrategy
(~ intelligent (~ intelligent OccamOccam’’ss razor)razor)
SOLVING THE SOLVING THE THERMOCHEMICAL NETWORKTHERMOCHEMICAL NETWORK
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
∆vapH(H2O)
H2
D0(H2)
CH
D0(CO) CO
CO + 1/2O2 → CO2
C(grph) + CO2 → 2CO
CO + H2O → CO2 + H2C(grph) + O2 → CO2
H2 + 1/2O2 → H2O(l)H2O(l)
H2O
CO2
O2
D0(O2)
O
C(grph)
∆sublH(C(grph))
•• TN preconditioningTN preconditioning::Bayesian logic, Bayesian logic, Nash games,Nash games,……
SOME ADVANTAGES OF SOME ADVANTAGES OF ACTIVE THERMOCHEMICAL TABLESACTIVE THERMOCHEMICAL TABLES
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
The solutions (∆fH°s) are superiorsuperior to conventional tables:values are globally consistentvalues are globally consistent with all input data uncertainties properly reflect all relationshipsuncertainties properly reflect all relationships presented as input
Allows painless propagation of new datapropagation of new data with all its consequencesOpens a new venue of rapid availability of latest informationrapid availability of latest information(including tentative data, if so desired)
Allows ““what ifwhat if”” teststests of:new datanew data for consistency (or lack thereof) with existing knowledgeeducationaleducational explorationsexplorations, including hypothetical data
By finding the ““weakest linksweakest links”” in the Network it can suggest new experiments/calculationssuggest new experiments/calculations that will have the highest impact on current knowledge (by itself a new paradigmnew paradigm)Supporting documents relating to input data (raw data, notes, pdf’s of papers, other pedigree information) are easily incorporated for examination
CMCS.org
Collaboratory for Collaboratory for MultiMulti--scale Chemical Science (CMCS)scale Chemical Science (CMCS)
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
•• CMCS is one of the CMCS is one of the SciDACSciDACNational National CollaboratoriesCollaboratories
•• Brings together scientists from Brings together scientists from various fields to develop an various fields to develop an open knowledge gridopen knowledge grid and the and the associated associated community portalcommunity portal for for multimulti--scale chemistry researchscale chemistry research
•• Uses Uses advanced collaboration, advanced collaboration, data management and data management and annotation technologiesannotation technologies
• The goal is to conquer current barriers to rapid sharingrapid sharing of validated informationvalidated information
X (cm)
R(c
m)
0 2 4 6 8 100
1
2
3
4 1
2
35
68
9
1004
2 711
CMCS.org
Collaboratory for Collaboratory for MultiMulti--scale Chemical Science (CMCS)scale Chemical Science (CMCS)
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
•• CMCS is one of the CMCS is one of the SciDACSciDACNational National CollaboratoriesCollaboratories
•• Brings together scientists from Brings together scientists from various fields to develop an various fields to develop an open knowledge gridopen knowledge grid and the and the associated associated community portalcommunity portal for for multimulti--scale chemistry researchscale chemistry research
•• Uses Uses advanced collaboration, advanced collaboration, data management and data management and annotation technologiesannotation technologies
• The goal is to conquer current barriers to rapid sharingrapid sharing of validated informationvalidated information
X (cm)
R(c
m)
0 2 4 6 8 100
1
2
3
4 1
2
35
68
9
1004
2 711
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
ACTIVE ACTIVE THERMOCHEMICAL TABLESTHERMOCHEMICAL TABLES
•• The current stable version ofThe current stable version of ATcTATcTis running as a is running as a web serviceweb service
CMCS
CMCS Portal
Shared Data Repository
Local Services/Grid Fabric
SAM
Web service
Active Table
CMCS/DAV
API
Notificatio
n
API
PortletAPI
•• Accessible from the Accessible from the CMCS portalCMCS portal••via an integrated via an integrated portletportlet
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
ACTIVE ACTIVE THERMOCHEMICAL TABLESTHERMOCHEMICAL TABLES
•• The current stable version ofThe current stable version of ATcTATcTis running as a is running as a web serviceweb service
CMCS
CMCS Portal
Shared Data Repository
Local Services/Grid Fabric
SAM
Web service
Active Table
CMCS/DAV
API
Notificatio
n
API
PortletAPI
•• Accessible from the Accessible from the CMCS portalCMCS portal••via an integrated via an integrated portletportlet
ACTIVE ACTIVE THERMOCHEMICAL TABLESTHERMOCHEMICAL TABLES
•• The current stable version ofThe current stable version of ATcTATcTis running as a is running as a web serviceweb service
•• Accessible from the Accessible from the CMCS portalCMCS portalvia an integrated via an integrated portletportlet
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
CH3
CMCS
ACTIVE ACTIVE THERMOCHEMICAL TABLESTHERMOCHEMICAL TABLES
•• The current stable version ofThe current stable version of ATcTATcTis running as a is running as a web serviceweb service
•• Accessible from the Accessible from the CMCS portalCMCS portalvia an integrated via an integrated portletportlet
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
CMCS
1CH2 + H2O → CH3 + OH
ACTIVE ACTIVE THERMOCHEMICAL TABLESTHERMOCHEMICAL TABLES
•• The current stable version ofThe current stable version of ATcTATcTis running as a is running as a web serviceweb service
•• Accessible from the Accessible from the CMCS portalCMCS portalvia an integrated via an integrated portletportlet
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
CMCS
Reaction network
7 8 9
H2O (l) H2O2 (l)
H2O H2O2
OH+ OH
H O
H2 O2
16 1718 19
20 2122 22a
15
3 4
23
5 6
2 1
10 11 12
14
137 8 97 8 9
H2O (l) H2O2 (l)
H2O H2O2
OH+ OH
H O
H2 O2
16 1718 1916 1718 19
20 2122 22a20 21
22 22a
1515
3 43 4
2323
5 65 6
22 11
10 11 12
10 11 12
1414
1313
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
ACTIVE ACTIVE THERMOCHEMICAL TABLESTHERMOCHEMICAL TABLES
•• The current stable version ofThe current stable version of ATcTATcTis running as a is running as a web serviceweb service
•• Accessible from the Accessible from the CMCS portalCMCS portalvia an integrated via an integrated portletportlet
CMCS.org
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
ACTIVE ACTIVE THERMOCHEMICAL TABLESTHERMOCHEMICAL TABLES
•• The current stable version ofThe current stable version of ATcTATcTis running as a is running as a web serviceweb service
•• Accessible from the Accessible from the CMCS portalCMCS portalvia an integrated via an integrated portletportlet
•• TheThe ATcTATcT backback--end end system consists of a system consists of a kernelkernel
CMCS.org
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
ACTIVE ACTIVE THERMOCHEMICAL TABLESTHERMOCHEMICAL TABLES
•• The current stable version ofThe current stable version of ATcTATcTis running as a is running as a web serviceweb service
•• Accessible from the Accessible from the CMCS portalCMCS portalvia an integrated via an integrated portletportlet
•• TheThe ATcTATcT backback--end end system consists of a system consists of a kernelkernel••and the and the underlying underlying collection of collection of thermochemically thermochemically relevant datarelevant data
CMCS.org
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
ACTIVE ACTIVE THERMOCHEMICAL TABLESTHERMOCHEMICAL TABLES
•• The current stable version ofThe current stable version of ATcTATcTis running as a is running as a web serviceweb service
•• Accessible from the Accessible from the CMCS portalCMCS portalvia an integrated via an integrated portletportlet
•• TheThe ATcTATcT backback--end end system consists of a system consists of a kernelkernel
•• The The ATcT kernelATcT kernel is quite complex; it is internally modular is quite complex; it is internally modular (eases program maintenance) and has so far ~ (eases program maintenance) and has so far ~ 60,000 lines60,000 lines of of Fortran 95 code (modifiable to HPF, which runs on parallel clustFortran 95 code (modifiable to HPF, which runs on parallel clusters, ers, needed for handling large networks)needed for handling large networks)
••and the and the underlying underlying collection of collection of thermochemically thermochemically relevant datarelevant data
CMCS.org
ATcT DATA ORGANIZATIONATcT DATA ORGANIZATION
•• The underlying The underlying data is data is organized in a organized in a number of number of LibrariesLibraries and and NotesNotes
•• LibrariesLibraries are large collections of data, typically generated by are large collections of data, typically generated by committees who oversee and anoint their scientific soundnesscommittees who oversee and anoint their scientific soundness
•• NotesNotes are lighter versions of Libraries, typically associated with are lighter versions of Libraries, typically associated with individual usersindividual users or or collaborative workgroupscollaborative workgroups
•• Main LibraryMain Library contains the contains the Core (Argonne) Thermochemical Network Core (Argonne) Thermochemical Network •• Auxiliary LibrariesAuxiliary Libraries contain data that reproduce information in contain data that reproduce information in
historical historical ““staticstatic”” tables tables for ready reference
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
CMCS.org
OH storyOH story……
• HH22OO →→ HH + OH+ OHD0(H-OH)
• OHOH →→ OO + H+ HD0(OH)
D0(H-OH)
∆Hat°0(H2O)
D0(OH)
∆Hf°0(OH)
Pioneering Science andTechnology
•• HH22OO →→ OO + 2 H+ 2 HD0(H-OH) + D0(OH) ≡∆Hat°0(H2O) =
= 76720.7 ± 8.3 cm-1
• ∆Hat°(H2O) depends only on∆Hf°(H2O), ∆Hf°(H), ∆Hf°(O)
rA-BC
ABC
ABC+
A + BC+
A + BC
AE0(BC+/ABC) IE(BC)
D0(A-BC)
rA-BC
ABC
ABC+
A + BC+
A + BC
AE0(BC+/ABC) IE(BC)
D0(A-BC)
AE0(BC+/ABC) IE(BC)
D0(A-BC)
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
FURTHER DEVELOPMENTSFURTHER DEVELOPMENTS……∆Hf°0(OH) = 8.86 8.86 ±± 0.16 kcal/mol0.16 kcal/molHerbon, Hanson, Golden, Bowman (2002)Ruscic et al. 8.85 8.85 ±± 0.07 kcal/mol0.07 kcal/mol
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
FURTHER DEVELOPMENTSFURTHER DEVELOPMENTS……∆Hf°0(OH) = 8.86 8.86 ±± 0.16 kcal/mol0.16 kcal/molHerbon, Hanson, Golden, Bowman (2002)Ruscic et al. 8.85 8.85 ±± 0.07 kcal/mol0.07 kcal/mol
D0(H-OH) = 41151 41151 ±± 5 cm5 cm--11
Harich, Hwang, Yang, Lin, Yang, Dixon (2000)Ruscic et al. 41128 41128 ±± 24 cm24 cm--11
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
FURTHER DEVELOPMENTSFURTHER DEVELOPMENTS……∆Hf°0(OH) = 8.86 8.86 ±± 0.16 kcal/mol0.16 kcal/molHerbon, Hanson, Golden, Bowman (2002)Ruscic et al. 8.85 8.85 ±± 0.07 kcal/mol0.07 kcal/mol
D0(H-OH) = 41151 41151 ±± 5 cm5 cm--11
Harich, Hwang, Yang, Lin, Yang, Dixon (2000)Ruscic et al. 41128 41128 ±± 24 cm24 cm--11
Gurvich et al. 41301 ± 17 cm-1
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
FURTHER DEVELOPMENTSFURTHER DEVELOPMENTS……∆Hf°0(OH) = 8.86 8.86 ±± 0.16 kcal/mol0.16 kcal/molHerbon, Hanson, Golden, Bowman (2002)Ruscic et al. 8.85 8.85 ±± 0.07 kcal/mol0.07 kcal/mol
D0(H-OH) = 41151 41151 ±± 5 cm5 cm--11
Harich, Hwang, Yang, Lin, Yang, Dixon (2000)Ruscic et al. 41128 41128 ±± 24 cm24 cm--11
23 cm-1
(0.066 kcal/mol)23.8 cm-1
100 ← 000
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
FURTHER DEVELOPMENTSFURTHER DEVELOPMENTS……∆Hf°0(OH) = 8.86 8.86 ±± 0.16 kcal/mol0.16 kcal/molHerbon, Hanson, Golden, Bowman (2002)Ruscic et al. 8.85 8.85 ±± 0.07 kcal/mol0.07 kcal/mol
D0(H-OH) = 41151 41151 ±± 5 cm5 cm--11
Harich, Hwang, Yang, Lin, Yang, Dixon (2000)Ruscic et al. 41128 41128 ±± 24 cm24 cm--11
23 cm-1
(0.066 kcal/mol)23.8 cm-1
100 ← 000
D0(HO-OH) = 17051.8 17051.8 ±± 3.4 cm3.4 cm--11
Luo, Fleming, Rizzo (1992) – but to use it we would need to rely on ∆Hf°(H2O2)
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
FURTHER DEVELOPMENTSFURTHER DEVELOPMENTS……∆Hf°0(OH) = 8.86 8.86 ±± 0.16 kcal/mol0.16 kcal/molHerbon, Hanson, Golden, Bowman (2002)Ruscic et al. 8.85 8.85 ±± 0.07 kcal/mol0.07 kcal/mol
D0(H-OH) = 41151 41151 ±± 5 cm5 cm--11
Harich, Hwang, Yang, Lin, Yang, Dixon (2000)Ruscic et al. 41128 41128 ±± 24 cm24 cm--11
23 cm-1
(0.066 kcal/mol)23.8 cm-1
100 ← 000
D0(HO-OH) = 17051.8 17051.8 ±± 3.4 cm3.4 cm--11
Luo, Fleming, Rizzo (1992) – but to use it we would need to rely on ∆Hf°(H2O2)
Joens (2001) D0(OH)/cm-1 ∆Hf°0(OH)/kcal/molRuscic et al. (prelim. letter) 35600 ± 30 ⇒ 8.829 ± 0.091
D0(H-OH) = 41141 ± 5 cm-1 ⇒ 35579 ± 11 ⇒ 8.892 (± 0.040)
D0(H2O2) = 17051.8 ± 3.4 cm-1⇒ 35589 ± 12 ⇒ 8.864 (± 0.042)
∆ = 0.028
⇒ 8.878 ± 0.029
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
FURTHER DEVELOPMENTSFURTHER DEVELOPMENTS……∆Hf°0(OH) = 8.86 8.86 ±± 0.16 kcal/mol0.16 kcal/molHerbon, Hanson, Golden, Bowman (2002)Ruscic et al. 8.85 8.85 ±± 0.07 kcal/mol0.07 kcal/mol
D0(H-OH) = 41151 41151 ±± 5 cm5 cm--11
Harich, Hwang, Yang, Lin, Yang, Dixon (2000)Ruscic et al. 41128 41128 ±± 24 cm24 cm--11
23 cm-1
(0.066 kcal/mol)23.8 cm-1
100 ← 000
D0(HO-OH) = 17051.8 17051.8 ±± 3.4 cm3.4 cm--11
Luo, Fleming, Rizzo (1992) – but to use it we would need to rely on ∆Hf°(H2O2)
Joens (2001) D0(OH)/cm-1 ∆Hf°0(OH)/kcal/molRuscic et al. (prelim. letter) 35600 ± 30 ⇒ 8.829 ± 0.091
D0(H-OH) = 41141 ± 5 cm-1 ⇒ 35579 ± 11 ⇒ 8.892 (± 0.040)
D0(H2O2) = 17051.8 ± 3.4 cm-1⇒ 35589 ± 12 ⇒ 8.864 (± 0.042)
∆ = 0.028
⇒ 8.878 ± 0.029
∆Hf°0(H2O2) from JANAF(298.15 K selection questionable,wrong conversion to 0 K)
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
FURTHER DEVELOPMENTSFURTHER DEVELOPMENTS……∆Hf°0(OH) = 8.86 8.86 ±± 0.16 kcal/mol0.16 kcal/molHerbon, Hanson, Golden, Bowman (2002)Ruscic et al. 8.85 8.85 ±± 0.07 kcal/mol0.07 kcal/mol
D0(H-OH) = 41151 41151 ±± 5 cm5 cm--11
Harich, Hwang, Yang, Lin, Yang, Dixon (2000)Ruscic et al. 41128 41128 ±± 24 cm24 cm--11
23 cm-1
(0.066 kcal/mol)23.8 cm-1
100 ← 000
D0(HO-OH) = 17051.8 17051.8 ±± 3.4 cm3.4 cm--11
Luo, Fleming, Rizzo (1992) – but to use it we would need to rely on ∆Hf°(H2O2)
Joens (2001) D0(OH)/cm-1 ∆Hf°0(OH)/kcal/molRuscic et al. (prelim. letter) 35600 ± 30 ⇒ 8.829 ± 0.091
D0(H-OH) = 41141 ± 5 cm-1 ⇒ 35579 ± 11 ⇒ 8.892 (± 0.040)
D0(H2O2) = 17051.8 ± 3.4 cm-1⇒ 35589 ± 12 ⇒ 8.864 (± 0.042)
∆ = 0.028
⇒ 8.878 ± 0.029
∆Hf°0(H2O2) from JANAF(298.15 K selection questionable,wrong conversion to 0 K)
4
55
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
FURTHER DEVELOPMENTSFURTHER DEVELOPMENTS……∆Hf°0(OH) = 8.86 8.86 ±± 0.16 kcal/mol0.16 kcal/molHerbon, Hanson, Golden, Bowman (2002)Ruscic et al. 8.85 8.85 ±± 0.07 kcal/mol0.07 kcal/mol
D0(H-OH) = 41151 41151 ±± 5 cm5 cm--11
Harich, Hwang, Yang, Lin, Yang, Dixon (2000)Ruscic et al. 41128 41128 ±± 24 cm24 cm--11
23 cm-1
(0.066 kcal/mol)23.8 cm-1
100 ← 000
D0(HO-OH) = 17051.8 17051.8 ±± 3.4 cm3.4 cm--11
Luo, Fleming, Rizzo (1992) – but to use it we would need to rely on ∆Hf°(H2O2)
Joens (2001) D0(OH)/cm-1 ∆Hf°0(OH)/kcal/molRuscic et al. (prelim. letter) 35600 ± 30 ⇒ 8.829 ± 0.091
D0(H-OH) = 41141 ± 5 cm-1 ⇒ 35579 ± 11 ⇒ 8.892 (± 0.040)
D0(H2O2) = 17051.8 ± 3.4 cm-1⇒ 35589 ± 12 ⇒ 8.864 (± 0.042)
∆ = 0.028
⇒ 8.878 ± 0.029
∆Hf°0(H2O2) from JANAF(298.15 K selection questionable,wrong conversion to 0 K)
8.920 ± 0.018
8.855 ± 0.027
0.065
8.900 ± 0.381
4
55
H2O
OH
H
?
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H2O
OH
H
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
7 8 9
H2O (l)
H2O
OH
H
H2 O2
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
7 8 9
H2O (l)
H2O
OH
H
H2 O2
5 6
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
7 8 9
H2O (l)
H2O
OH
H
H2 O2
OH+
16 1718 19
5 6
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
7 8 9
H2O (l)
H2O
OH
H
H2 O2
OH+
16 1718 19
20 2122 22a
5 6
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
7 8 9
H2O (l)
H2O
OH
H
H2 O2
OH+
16 1718 19
20 2122 22a
O
3 4
5 6
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
7 8 9
H2O (l)
H2O
OH
H
H2 O2
OH+
16 1718 19
20 2122 22a
O
3 4
5 6
2 1
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
7 8 9
H2O (l)
H2O
OH
H
H2 O2
OH+
16 1718 19
20 2122 22a
15
O
3 4
5 6
2 1
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
7 8 9
H2O (l)
H2O
OH
H
H2 O2
OH+
16 1718 19
20 2122 22a
15
O
3 4
23
5 6
2 1
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
7 8 9
H2O (l)
H2O
OH
H
H2 O2
OH+
16 1718 19
20 2122 22a
15
O
3 4
23
5 6
2 1
H2O2
14
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
7 8 9
H2O (l)
H2O
OH
H
H2 O2
OH+
16 1718 19
20 2122 22a
15
O
3 4
23
5 6
2 1
H2O2 (l)
10 11 12
H2O2
14
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
7 8 9
H2O (l)
H2O
OH
H
H2 O2
OH+
16 1718 19
20 2122 22a
15
O
3 4
23
5 6
2 1
H2O2 (l)
10 11 12
H2O2
14
13
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
RESULTS OF ATcT RESULTS OF ATcT O/H TN ANALYSISO/H TN ANALYSIS
• ∆Hf°0(OH) = 8.858.8599 ±± 0.010.0177 kcal/molkcal/mol(cf. Ruscic et al. 8.856 ± 0.070 kcal/mol)
• D0(H-OH) = 41129 41129 ±± 7 cm7 cm--11
(cf. Ruscic et al. 41128 ± 24 cm-1)• D0(OH) = 35590 35590 ±± 12 cm12 cm--11
(cf. Ruscic et al. 35593 ± 25 cm-1)
• Statistical analysis points to the following “optimistic” uncertainties:• D0(OH), Carlone & Dalby 11.3 × 15 cm-1
•• DD00(H(H--OH), OH), HarichHarich et al.et al. 4.54.5 ×× 5 cm5 cm--11
• ∆vapH°298(H2O2), Edgerton et al. 2nd Law 1.4 × 0.74 kcal/mol• D0(OH), Barrow 1.4 × 100 cm-1
• ∆vapH°298(H2O), Keenan et al., old steam tab. 1.2 × 0.002 kcal/mol
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
ATcT HYPOTHESIS TEST (ATcT HYPOTHESIS TEST (““WHAT IFWHAT IF”” ))
•• HypothesisHypothesis: all photoionization experiments are off:all AE0(OH+/H2O) increased by 23.8 cm-1
• Statistical analysis points to the following “optimistic” uncertainties:• D0(OH), Carlone & Dalby 11.2 × 15 cm-1
•• DD00(H(H--OH), OH), HarichHarich et al.et al. 4.14.1 ×× 5 cm5 cm--11
•• AEAE00(OH(OH++/H/H22O), PFIO), PFI--PE BerkeleyPE Berkeley 1.51.5 ×× 0.002 eV0.002 eV• ∆vapH°298(H2O2), Edgerton et al. 2nd Law 1.4 × 0.74 kcal/mol• D0(OH), Barrow 1.4 × 100 cm-1
• ∆vapH°298(H2O), Keenan et al., old steam tab. 1.2 × 0.002 kcal/mol• ∆vapH°298(H2O2), Edgerton et al. 3rd Law 1.1 × 0.038 kcal/mol
• ∆Hf°0(OH) = 8.868.8633 ±± 0.000.0099 kcal/molkcal/mol(cf. unbiased ATcT 8.859 ± 0.017 kcal/mol)
• D0(H-OH) = 41130 41130 ±± 4 cm4 cm--11
(cf. unbiased ATcT 41129 ± 7 cm-1)• D0(OH) = 35588 35588 ±± 6 cm6 cm--11
(cf. unbiased ATcT 35590 ± 12 cm-1)
⌧Though the network does not allow the values to stray away too much, this solution has to be rejected because it’s based on a hypothesis demonstrated to be incorrect
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
BOTTOM LINEBOTTOM LINE……
∆fH°298(OH)
36.5
37.0
37.5
38.0
38.5
39.0
39.5
40.0
40.5
kJ/m
ol
JANAF
Gurvich et
ATcT 1.19CoreTN 1.032
Ruscic et al
JANAF
Gurvich et al.
Ruscic et al.ATcT 1.25CoreTN 1.040
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
A few corollariesA few corollaries……HH22OO22
∆fH°298(H2O2)
-137.0
-136.0
-135.0
kJ/m
ol
JANAF
Gurvich et al.ATcT 1.19
CoreTN 1.032
Gurvich et al.
JANAF
ATcT 1.25CoreTN 1.040
A few corollariesA few corollaries…… OO33
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
∆fH°298(O3)
140.0
141.0
142.0
143.0
144.0
kJ/m
ol
JANAF
Gurvich et
ATcT 1.19CoreTN 1.032
Taniguchi et al
JANAF
Gurvich et al.
Taniguchi et al
ATcT 1.25CoreTN 1.040
A few corollariesA few corollaries…… OO33
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
∆fH°298(O3)
140.0
141.0
142.0
143.0
144.0
kJ/m
ol
JANAF
Gurvich et
ATcT 1.19CoreTN 1.032
Taniguchi et al
JANAF
Gurvich et al.
Taniguchi et al
ATcT 1.25CoreTN 1.040
∆fH°298(O3)
141.3
141.5
141.7
141.9
142.1
kJ/m
ol
JANAF
Gurvich et
ATcT 1.19CoreTN 1.032
Taniguchi et alTaniguchi et al
ATcT 1.25CoreTN 1.040
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
A few corollariesA few corollaries…… OO
∆fH°298(O)
249.0
249.1
249.2
249.3
249.4
kJ/m
ol
CODATA
ATcT 1.19CoreTN 1.032
CODATA, Gurvich et al., JANAF, …
ATcT 1.25CoreTN 1.040
∆fH°298(O)
249.10
249.20
249.30
kJ/m
ol
CODATA
ATcT 1.19CoreTN 1.032
CODATA, Gurvich et al., JANAF, …
ATcT 1.25CoreTN 1.040
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
A few corollariesA few corollaries…… HH
∆fH°298(H)
217.99
218.00
218.01
kJ/m
ol
CODATA
ATcT 1.19CoreTN 1.032
CODATA, Gurvich et al., JANAF, …
ATcT 1.25CoreTN 1.040
∆fH°298(H)
217.993
217.998
218.003
kJ/m
ol
CODATA
ATcT 1.19CoreTN 1.032
CODATA, Gurvich et al., JANAF, …
ATcT 1.25CoreTN 1.040
THE C (g) QUESTIONTHE C (g) QUESTION
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
It’s a 50-year old puzzle…∆fH°(C(gas)) ≡≡ ∆sublH°(C(graphite))∆fH°(C(gas)) is one of the CODATA “key” thermochemical quantitiesInter alia, it is used as a fixed reference point for carbon by all ab initio computations (such as Gn, Wn, etc) that produce enthalpies of formation via atomization energiesEarly measurements attempted to determine∆sublH°(C(graphite)) via measurements of equilibriaCODATA used D0(CO), once it got settled…
THE C (g) QUESTIONTHE C (g) QUESTION
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
H
C
D0(CH)
∆vapH(H2O)
H2
D0(H2)
CH
D0(CO) CO
CO + 1/2O2 → CO2
C(grph) + CO2 → 2CO
CO + H2O → CO2 + H2C(grph) + O2 → CO2
H2 + 1/2O2 → H2O(l)H2O(l)
H2O
CO2
O2
D0(O2)
O
C(grph)
∆sublH(C(grph))
The original D0(CO) is a “weak link”
THE DTHE D00(CO) QUESTION(CO) QUESTION
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
• A. E. Douglas and C. K. Moller, Can. J. Phys. 33, 125 (1955)
• The uncertainty addressed at the time was whether D0(CO) is: ~ 11.1 eV~ 11.1 eV from apparent predissociation at v' = 0, J > 37
of the Ångström system of CO (B1Σ ← of A1Π), or~ 9.6 eV~ 9.6 eV suggested by electron impact and supported by
observed weakening of some lines at v = 7, 8, 9 in the fourth positive system (A 1Π ← of X1Σ) of CO
or some yet different value
THE DTHE D00(CO) QUESTION(CO) QUESTION
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
• A. E. Douglas and C. K. Moller, Can. J. Phys. 33, 125 (1955)
• 12CO B1Σ predissociation clearly observed between J = 37 and 38 in v = 0J = 17 and 18 in v = 1
13CO B1Σ predissociation clearly observed between J = 39 and 40 in v = 0J = 19 and 20 in v = 1
DD00(CO) = (CO) = 89595 89595 ±± 30 cm30 cm--11
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
LIMITING CURVES OF DISSOCIATION of COLIMITING CURVES OF DISSOCIATION of CO12C16O and 13C16O - Limiting Curves of Dissociation
90600
90700
90800
90900
91000
91100
0 200 400 600 800 1000 1200 1400 1600 1800 2000
J(J+1)
De /
cm
-1
A. E. Douglas and C. K. Moller, Can. J. Phys. 33, 125 (1955)De(CO) = 90677 ± 30 cm-1 ⇒ D0(CO) = 89595 ± 30 cm-1
CO B 1Σ
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
12C16O and 13C16O - Limiting Curves of Dissociation
90600
90700
90800
90900
91000
91100
0 200 400 600 800 1000 1200 1400 1600 1800 2000
J(J+1)
De /
cm
-1
LIMITING CURVES OF DISSOCIATION of COLIMITING CURVES OF DISSOCIATION of CO
CO B 1Σ
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
12C16O and 13C16O - Limiting Curves of Dissociation
90600
90700
90800
90900
91000
91100
0 200 400 600 800 1000 1200 1400 1600 1800 2000
J(J+1)
De /
cm
-1
A. E. Douglas and C. K. Moller, Can. J. Phys. 33, 125 (1955)De(CO) = 90677 ± 30 cm-1 ⇒ D0(CO) = 89595 ± 30 cm-1
Ruscic et al. unpub (2003)De(CO) = 90739 ± 30 cm-1 ⇒ D0(CO) = 89651 ± 30 cm-1
LIMITING CURVES OF DISSOCIATION of COLIMITING CURVES OF DISSOCIATION of CO
CO B 1ΣDe(CO) = 90739 ± 30 cm-1 ⇒ D0(CO) = 89660 ± 30 cm-1De(CO) = 90739 ± 30 cm-1 ⇒ D0(CO) = 89660 ± 30 cm-1
De(CO) = 90677 ± 30 cm-1 ⇒ D0(CO) = 89595 ± 30 cm-1
DD00(CO)(CO)
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
From reinterpretation of spectroscopic data:
De(CO) = 90677 ± 30 cm-1 ⇒ D0(CO) = 89595 ± 30 cm-1
DDee(CO(CO) = 90739 ) = 90739 ±± 30 cm30 cm--11 ⇒⇒ DD00(CO) = 89660 (CO) = 89660 ±± 30 cm30 cm--11
(uncert. reflects a slight discrepancy between 12CO and 13CO)
• Best estimate from state of the art ab initio calculations:(using converged levels of var. methods, including higher order coupled cluster and full configuration interaction benchmarks extrapolated to complete basis set full configuration interaction limit plus corrections for relativistic effects and diagonal Born-Oppenheimer correction to reduce remaining computational errors):
DDee(CO(CO) = 90758 ) = 90758 ±± 30 cm30 cm--11 ⇒⇒ DD00(CO) = 89679 (CO) = 89679 ±± 30 cm30 cm--11
• We are currently pursuing additional experiments at ALSin collaboration with C.-Y. Ng (measurements are in progress)
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
∆fH°298(C)
716.0
716.5
717.0
717.5
718.0
kJ/m
ol
CODATA
ATcT 1.19CoreTN 1.032
THE C (g) QUESTIONTHE C (g) QUESTION
CODATA, Gurvich et al., JANAF, …
ATcT 1.25CoreTN 1.040
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
A couple of corollariesA couple of corollaries……
∆fH°298(CO2)
-394.0
-393.5
-393.0
kJ/m
ol
CODATA
ATcT 1.19CoreTN 1.032
∆fH°298(CO)
-111.0
-110.5
-110.0
kJ/m
ol
CODATA
ATcT 1.19CoreTN 1.032
CODATA, Gurvich et al., JANAF, …
ATcT 1.25CoreTN 1.040
CODATA, Gurvich et al., JANAF, …
ATcT 1.25CoreTN 1.040
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
NN
∆fH°298(N)
472.0
472.5
473.0
473.5
kJ/m
ol
CODATA
ATcT 1.19CoreTN 1.032
CODATA, Gurvich et al., JANAF, …
ATcT 1.25CoreTN 1.040
DD00(N(N22)),,the primary the primary
determination determination leading to leading to ∆∆ffHH°°(N(N),),
is ais a““weak linkweak link””
limiting limiting the accuracy the accuracy
of the of the thermochemistry thermochemistry
ofof N N and through it ofand through it of
NONOxx species,species,as well as many as well as many
other other NN--containing containing
speciesspecies
NO AND NONO AND NO22
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
∆fH°298(NO2)
32.0
32.5
33.0
33.5
34.0
34.5
35.0
kJ/m
ol
JANAF
Gurvich et al. ATcT 1.19CoreTN 1.032
∆fH°298(NO)
89.5
90.0
90.5
91.0
91.5
92.0
92.5
kJ/m
ol
JANAF
Gurvich et al.
ATcT 1.19CoreTN 1.032
JANAF
Gurvich et al.
ATcT 1.25CoreTN 1.040
JANAF
Gurvich et al. ATcT 1.25CoreTN 1.040
HOHO22
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
∆fH°298(HO2)
-5.0
0.0
5.0
10.0
15.0
20.0
kJ/m
ol
JANAF
Gurvich et al.
ATcT 1.19CoreTN 1.032
Lineberger2001
Ruscic 1998
Fisher & Armintrout 1998
JANAF
Gurvich et al.
Lee & HowardShum &Benson
Fisher & Armentrout
Ruscic &Litorja
Linebergeret al
ATcT 1.25CoreTN 1.040
““Howard Howard reactionreaction””
OH + NOOH + NO22 →→HOHO22 + NO+ NO
ATcT thermo ATcT thermo + new kinetic + new kinetic experiments experiments
(J. Michael, ANL):(J. Michael, ANL):the reverse rate the reverse rate
was indeed off by was indeed off by a factor of 2!a factor of 2!
∆fH°298(CH2O)
-117
-116
-115
-114
-113
-112
-111
-110
-109
-108
kJ/m
ol
JANAF
Gurvich et al.
ATcT 1.19CoreTN 1.032
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
CHCH22OO
JANAF
Gurvich et al. ATcT 1.25CoreTN 1.040
∆fH°298(HCO)
34
38
42
46
50
kJ/m
ol
JANAF
Gurvich et al.
ATcT 1.19CoreTN 1.032
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
HCOHCO
JANAF
Gurvich et al.
ATcT 1.25CoreTN 1.040
∆fH°298(CH4)
-75.5
-75.0
-74.5
-74.0
kJ/m
ol
JANAF
Gurvich et al.
ATcT 1.19CoreTN 1.032
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
CHCH44
JANAF
Gurvich et al.
ATcT 1.25CoreTN 1.040
∆fH°298(CH3)
144.5
145.0
145.5
146.0
146.5
147.0
kJ/m
ol
JANAF
Gurvich et al.
ATcT 1.19CoreTN 1.032
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
CHCH33
JANAF
Gurvich et al.
ATcT 1.25CoreTN 1.040
∆fH°298(CH2)
380
385
390
395
kJ/m
ol
JANAF
Gurvich et al.
ATcT 1.19CoreTN 1.032
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
CHCH22
JANAF
Gurvich et al. ATcT 1.25CoreTN 1.040
∆fH°298(CH)
570
575
580
585
590
595
600
605
610
615
kJ/m
ol
JANAF
Gurvich et al.
ATcT 1.19CoreTN 1.032
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
CHCH
JANAF
Gurvich et al.
ATcT 1.25CoreTN 1.040
∆fH°298(NH3)
-47.0
-46.5
-46.0
-45.5
-45.0
kJ/m
ol
JANAF
Gurvich et al.
ATcT 1.19CoreTN 1.032
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
NHNH33
CODATA,JANAF, Gurvich et al
ATcT 1.25CoreTN 1.040
∆fH°298(NH2)
170
175
180
185
190
195
200
205
210
kJ/m
ol
JANAF
Gurvich et al.
ATcT 1.19CoreTN 1.032
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
NHNH22
JANAF Gurvich et al.
ATcT 1.25CoreTN 1.040
∆fH°298(NH)
345
350
355
360
365
370
375
380
385
390
395
400
kJ/m
ol
JANAF
Gurvich et al.
ATcT 1.19CoreTN 1.032
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
NHNH
JANAF
Gurvich et al.ATcT 1.25
CoreTN 1.040
Interplay of ATcT with Interplay of ATcT with MultiMulti--Scale Chemical ScienceScale Chemical Science
- ATcT are a provider of information to other scales
ATcT
KineticRates
ChemicalMechanisms
MolecularScale
WorkingGroups - ATcT are also
a consumerof information from other scales
CMCS.org
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
THE VISION:THE VISION:STACKED ACTIVE TABLESSTACKED ACTIVE TABLES
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
ATcT
Kinetic Rates AT
Fundamental Constants AT
Chemical Mechanisms AT
Reduced Mechanisms AT
Spectro-scopic AT
Pioneering Science andTechnology
Office of ScienceU.S. DEPARTMENT
OF ENERGY
Thank you for your attention!Thank you for your attention!
CMCS
visit: http://cmcs.org
• go to the Portal• open an account• join one of the ATcT groups• explore beta tester data/software ATcT version
Questions, suggestions,to contribute new data,
or to get latest thermochemistry:[email protected]