argonne national laboratory, argonne, il

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?



OF ENERGY

WHAT ARE WHAT ARE ACTIVE THERMOCHEMICAL TABLES?ACTIVE THERMOCHEMICAL TABLES?



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?



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?



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



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°°



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



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



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



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 ?



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CH




OF ENERGY

H

C

D0(CH)CH




OF ENERGY

H

C

D0(CH)

H2

D0(H2)

CH




OF ENERGY

H

C

D0(CH)

H2

D0(H2)

CH

D0(CO) CO

O




OF ENERGY

H

C

D0(CH)

H2

D0(H2)

CH

D0(CO) CO

O2

D0(O2)

O




OF ENERGY

H

C

D0(CH)

H2

D0(H2)

CH

D0(CO) CO

CO + 1/2O2 → CO2

CO2

O2

D0(O2)

O




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)




OF ENERGY

H

C

D0(CH)

H2

D0(H2)

CH

D0(CO) CO

CO + 1/2O2 → CO2


CO + H2O → CO2 + H2H2O

CO2

O2

D0(O2)

O

C(grph)




OF ENERGY

H

C

D0(CH)

H2

D0(H2)

CH

D0(CO) CO

CO + 1/2O2 → CO2


CO + H2O → CO2 + H2C(grph) + O2 → CO2 H2O

CO2

O2

D0(O2)

O

C(grph)




OF ENERGY

H

C

D0(CH)

∆vapH(H2O)

H2

D0(H2)

CH

D0(CO) CO

CO + 1/2O2 → CO2


CO + H2O → CO2 + H2C(grph) + O2 → CO2

H2O(l)

H2O

CO2

O2

D0(O2)

O

C(grph)




OF ENERGY

H

C

D0(CH)

∆vapH(H2O)

H2

D0(H2)

CH

D0(CO) CO

CO + 1/2O2 → CO2



H2 + 1/2O2 → H2O(l)H2O(l)

H2O

CO2

O2

D0(O2)

O

C(grph)




OF ENERGY

H

C

D0(CH)

∆vapH(H2O)

H2

D0(H2)

CH

D0(CO) CO

CO + 1/2O2 → CO2



H2 + 1/2O2 → H2O(l)H2O(l)

H2O

CO2

O2

D0(O2)

O

C(grph)

∆sublH(C(grph))




OF ENERGY

H

C

D0(CH)

∆vapH(H2O)

H2

D0(H2)

CH

D0(CO) CO

CO + 1/2O2 → 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




OF ENERGY

H

C

D0(CH)

∆vapH(H2O)

H2

D0(H2)

CH

D0(CO) CO

CO + 1/2O2 → 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,…)




OF ENERGY

H

C

D0(CH)

∆vapH(H2O)

H2

D0(H2)

CH

D0(CO) CO

CO + 1/2O2 → 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




OF ENERGY

H

C

D0(CH)

∆vapH(H2O)

H2

D0(H2)

CH

D0(CO) CO

CO + 1/2O2 → 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) ::




OF ENERGY

H

C

D0(CH)

∆vapH(H2O)

H2

D0(H2)

CH

D0(CO) CO

CO + 1/2O2 → 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


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



OF ENERGY


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



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



OF ENERGY

H

C

D0(CH)

∆vapH(H2O)

H2

D0(H2)

CH

D0(CO) CO

CO + 1/2O2 → 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



OF ENERGY

H

C

D0(CH)

∆vapH(H2O)

H2

D0(H2)

CH

D0(CO) CO

CO + 1/2O2 → 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



OF ENERGY

H

C

D0(CH)

∆vapH(H2O)

H2

D0(H2)

CH

D0(CO) CO

CO + 1/2O2 → 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



OF ENERGY

H

C

D0(CH)

∆vapH(H2O)

H2

D0(H2)

CH

D0(CO) CO

CO + 1/2O2 → 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



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)



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



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



•• Accessible from the Accessible from the CMCS portalCMCS portalvia an integrated via an integrated portletportlet



OF ENERGY

CH3

CMCS






OF ENERGY

CMCS

1CH2 + H2O → CH3 + OH






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



OF ENERGY




CMCS.org



OF ENERGY




•• TheThe ATcTATcT backback--end end system consists of a system consists of a kernelkernel

CMCS.org



OF ENERGY




•• 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



OF ENERGY




•• 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



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)


•• 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)



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



OF ENERGY


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



OF ENERGY


D0(H-OH) = 41151 41151 ±± 5 cm5 cm--11


Gurvich et al. 41301 ± 17 cm-1



OF ENERGY


D0(H-OH) = 41151 41151 ±± 5 cm5 cm--11


23 cm-1

(0.066 kcal/mol)23.8 cm-1

100 ← 000



OF ENERGY


D0(H-OH) = 41151 41151 ±± 5 cm5 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)



OF ENERGY


D0(H-OH) = 41151 41151 ±± 5 cm5 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


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



OF ENERGY


D0(H-OH) = 41151 41151 ±± 5 cm5 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



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)



OF ENERGY


D0(H-OH) = 41151 41151 ±± 5 cm5 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



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


4

55



OF ENERGY


D0(H-OH) = 41151 41151 ±± 5 cm5 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



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


8.920 ± 0.018

8.855 ± 0.027

0.065

8.900 ± 0.381

4

55

H2O

OH

H

?



OF ENERGY

H2O

OH

H



OF ENERGY

7 8 9

H2O (l)

H2O

OH

H

H2 O2



OF ENERGY

7 8 9

H2O (l)

H2O

OH

H

H2 O2

5 6



OF ENERGY

7 8 9

H2O (l)

H2O

OH

H

H2 O2

OH+

16 1718 19

5 6



OF ENERGY

7 8 9

H2O (l)

H2O

OH

H

H2 O2

OH+

16 1718 19

20 2122 22a

5 6



OF ENERGY

7 8 9

H2O (l)

H2O

OH

H

H2 O2

OH+

16 1718 19

20 2122 22a

O

3 4

5 6



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



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



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



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



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



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



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



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



OF ENERGY



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



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


A few corollariesA few corollaries…… OO33



OF ENERGY

∆fH°298(O3)

140.0

141.0

142.0

143.0

144.0

kJ/m

ol

JANAF

Gurvich et


Taniguchi et al

JANAF

Gurvich et al.

Taniguchi et al


A few corollariesA few corollaries…… OO33



OF ENERGY

∆fH°298(O3)

140.0

141.0

142.0

143.0

144.0

kJ/m

ol

JANAF

Gurvich et


Taniguchi et al

JANAF

Gurvich et al.

Taniguchi et al


∆fH°298(O3)

141.3

141.5

141.7

141.9

142.1

kJ/m

ol

JANAF

Gurvich et


Taniguchi et alTaniguchi et al




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


CODATA, Gurvich et al., JANAF, …


∆fH°298(O)

249.10

249.20

249.30

kJ/m

ol

CODATA






OF ENERGY

A few corollariesA few corollaries…… HH

∆fH°298(H)

217.99

218.00

218.01

kJ/m

ol

CODATA




∆fH°298(H)

217.993

217.998

218.003

kJ/m

ol

CODATA




THE C (g) QUESTIONTHE C (g) QUESTION



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…




OF ENERGY

H

C

D0(CH)

∆vapH(H2O)

H2

D0(H2)

CH

D0(CO) CO

CO + 1/2O2 → 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



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



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



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



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



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)



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)



OF ENERGY

∆fH°298(C)

716.0

716.5

717.0

717.5

718.0

kJ/m

ol

CODATA







OF ENERGY

A couple of corollariesA couple of corollaries……

∆fH°298(CO2)

-394.0

-393.5

-393.0

kJ/m

ol

CODATA


∆fH°298(CO)

-111.0

-110.5

-110.0

kJ/m

ol

CODATA








OF ENERGY

NN

∆fH°298(N)

472.0

472.5

473.0

473.5

kJ/m

ol

CODATA




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



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.


JANAF

Gurvich et al.


JANAF


HOHO22



OF ENERGY

∆fH°298(HO2)

-5.0

0.0

5.0

10.0

15.0

20.0

kJ/m

ol

JANAF

Gurvich et al.


Lineberger2001

Ruscic 1998

Fisher & Armintrout 1998

JANAF

Gurvich et al.

Lee & HowardShum &Benson

Fisher & Armentrout

Ruscic &Litorja

Linebergeret al


““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.




OF ENERGY

CHCH22OO

JANAF


∆fH°298(HCO)

34

38

42

46

50

kJ/m

ol

JANAF

Gurvich et al.




OF ENERGY

HCOHCO

JANAF

Gurvich et al.


∆fH°298(CH4)

-75.5

-75.0

-74.5

-74.0

kJ/m

ol

JANAF

Gurvich et al.




OF ENERGY

CHCH44

JANAF

Gurvich et al.


∆fH°298(CH3)

144.5

145.0

145.5

146.0

146.5

147.0

kJ/m

ol

JANAF

Gurvich et al.




OF ENERGY

CHCH33

JANAF

Gurvich et al.


∆fH°298(CH2)

380

385

390

395

kJ/m

ol

JANAF

Gurvich et al.




OF ENERGY

CHCH22

JANAF


∆fH°298(CH)

570

575

580

585

590

595

600

605

610

615

kJ/m

ol

JANAF

Gurvich et al.




OF ENERGY

CHCH

JANAF

Gurvich et al.


∆fH°298(NH3)

-47.0

-46.5

-46.0

-45.5

-45.0

kJ/m

ol

JANAF

Gurvich et al.




OF ENERGY

NHNH33

CODATA,JANAF, Gurvich et al


∆fH°298(NH2)

170

175

180

185

190

195

200

205

210

kJ/m

ol

JANAF

Gurvich et al.




OF ENERGY

NHNH22

JANAF Gurvich et al.


∆fH°298(NH)

345

350

355

360

365

370

375

380

385

390

395

400

kJ/m

ol

JANAF

Gurvich et al.




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



OF ENERGY

THE VISION:THE VISION:STACKED ACTIVE TABLESSTACKED ACTIVE TABLES



OF ENERGY

ATcT

Kinetic Rates AT

Fundamental Constants AT

Chemical Mechanisms AT

Reduced Mechanisms AT

Spectro-scopic AT



OF ENERGY

Thank you for your attention!Thank you for your attention!

CMCS

visit: http://cmcs.org

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