DEVELOPMENT OF METHODOLOGIES FOR THE ACCURATE ESTIMATION OF REACTION ...

222 Pages·2013·8.4 MB·English

Tesi di Dottorato di DANIELA POLINO
Matricola 753430

POLITECNICO DI MILANO

DEVELOPMENT OF

METHODOLOGIES FOR THE
DIPARTIMENTO
ACCURATE ESTIMATION OF
DI
CHIMICA, REACTION RATE COEFFICIENTS
MATERIALI
E
INGEGNERIA CHIMICA
“Giulio Natta”

Dottorato di Ricerca in
Chimica Industriale e
Ingegneria Chimica (CII)

XXV ciclo
2010 - 2012
Coordinatore: prof. Tiziano Faravelli

Tutore: prof. Maurizio Masi

Relatore: prof. Carlo Cavallotti

Your eyes are windows into your body
If you open your eyes in wonder and belief, your body fills up with light
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Acknowledgements
I would like to thank all the people that have been with me in the last three years, which have
been probably the best three years of my life so far.
First, I am deeply grateful to my advisor Prof. Carlo Cavallotti. To work with you has been a
great pleasure and most times a lot of fun. Thank you for your teachings and your guidance; they
have affected and shaped my life. You have believed in me and challenged me to go beyond my
limits and never settle for less than excellence. Thank you.
I want to thank also Dr. Stephen Klippenstein. Thank you for the opportunity I have been given
to work with you. Thank you for your precious help and assistance during my visit at Argonne Na-
tional Laboratory. Along with Dr. Stephen Klippenstein I want to thank all the scientists in the
chemical dynamics group at ANL that I have met: Steve, Larry, Yuri, Joe, Glen, Ron, Al, Rob,
Raghu and last, but not least I cannot forget Jim, the funniest officemate I have ever had! Thanks to
all of you. It has been a great privilege to meet you.
I want to thank Franco the person that shared with me this adventure from the closest side.
Thank you for your patience, for your encouragement, for being there when I needed someone to
rely on. I am looking forward to live more of these adventures, as long as we are together.
Special thanks are for my parents and for my brother Davide. You do not know just how im-
portant your presence has been these last three years. You are the best family I could ever wish for!
I want to thank the CFA group and the friends and colleagues that have been with me during
these three years and made this experience unique: Filippo, Marco, Matteo, Danilo, Tommaso,
Stefano, Raffaele, Vangelis, Tushar, Claudio, Ruggiero e Silvia.
I want also to thank the people I have met in Chicago during my visit at Argonne that have as-
sisted me to settle down and enjoy my permanence there. Thank you to my new second mom Lina,
Sebastian and Martha, Martin, Christian, Colin, Francesc, Chris, Patrick and Gokhan, Amit and
Mike.
Finally, I want to thank the One who put this dream in my heart and made it become true. The
One who has been with me every single moment, never letting me go. Thank you Jesus, because in
the end I owe it all to you.

Daniela

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Publications and Conferences

1. On the kinetics of the C H + C H reaction
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Cavallotti C., Polino D., Proceedings of the Combustion Institute, 2012 in
press

2. Is Quantum Tunneling Relevant in Free Radical Polymerization?
Cuccato D., Dossi M., Polino D., Cavallotti C., Moscatelli D. Macromolecular
Reaction Engineering , 6, 496 (2012)

3. Analysis of Some Reaction Pathways Active during Cyclopentadiene Pyrolysis
Cavallotti C., Polino D., Frassoldati A., Ranzi E. J. Phys. Chem. A, 116, 3313
(2012)

4. Toluene and benzyl decomposition mechanisms: elementary reactions and ki-
netic simulations
Derudi M., Polino D. and Cavallotti C., Phys Chem Chem Phys , 13, 21308
(2011)

5. Fulvenallene Decomposition Kinetics
Polino D. and Cavallotti C., J. Phys. Chem. A, 115, 10281 (2011)

6. Analysis of the Reactivity on the C H Potential Energy Surface
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Polino D., Famulari A. and Cavallotti C., J. Phys. Chem. A, 115, 7928 (2011)

7. Theoretical investigation of germane and germylene decomposition kinetics
Polino D., Barbato A. and Cavallotti C., Phys. Chem. Chem. Phys., 12, 10622
(2010)

8. An Ab Initio RRKM/Master Equation Investigation of SiH and GeH Decom-
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position Kinetics Using a Kinetic Monte Carlo Approach
Cavallotti C., Polino D. and Barbato B., ECS Transactions 25 (8 PART 1),
445-452 (2009)

9. On the kinetics of the C H + C H reaction. Cavallotti C. and Polino D. , 34th
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International Symposium on Combustion, Warsaw, University of Technology,
Poland, July 29 – August 3 2012

10. An RRKM/ME analysis of the decomposition kinetics active on the C H poten-
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tial energy surface. Polino D., Derudi M., Cavallotti C., 7th International Con-
ference on Chemical Kinetics, MIT, Cambridge, MA, US, 10-14 July 2011

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11. Predictive theory for the addition kinetics of 1CH with unsaturated hydrocar-
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bons. Polino D., Georgievskii Y., Klippenstein S.J. 22nd International Sympo-
sium on Gas Kinetics, Boulder, CO, US, 18-22 June 2012

12. Reactivity of silicon surfaces in presence of adsorbed hydrogen and chlorine.
Cavallotti C. and Polino D. 241st National Meeting and Exposition of the
American Chemical Society (ACS), Anaheim, CA, US, 27-31 March 2011

13. An ab initio RRKM/master equation investigation of SiH and GeH decompo-
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sition kinetics using a kinetic Monte Carlo approach. Cavallotti C. Polino D.,
Barbato A. 17th International Chemical Vapor Deposition Symposium 216th
Meeting of the Electrochemical Society; Vienna; 4-9 October 2009
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Table of Contents
Acknowledgements .......................................................................................................................... iii
Publications and Conferences .......................................................................................................... v
Table of Contents ........................................................................................................................... vii
List of Figures .................................................................................................................................. xi
List of Tables ................................................................................................................................. xix
Abstract .......................................................................................................................................... xxi
1 Introduction .................................................................................................................................... 1
2 Theoretical Gas Phase Chemical Kinetics: The State of the Art ............................................... 3
2.1. Quantum Mechanics in Theoretical Kinetics ...................................................................... 3
2.2. Kinetic Theories .................................................................................................................. 6
2.2.1. Basic Concepts ............................................................................................................ 6
2.2.2. Transition State Theory ............................................................................................... 9
2.2.3. Microscopic Rate Coefficients – The RRKM theory ................................................ 12
2.2.4. The Variable Reaction Coordinate – Transition State Theory .................................. 16
2.2.5. Solution of the Master Equation ................................................................................ 16
3 Methods ......................................................................................................................................... 19
3.1. Computational Quantum Chemistry .................................................................................. 20
3.1.1. The Hamiltonian Operator......................................................................................... 20
3.1.2. The Born-Oppenheimer Approximation ................................................................... 21
3.1.3. Hartree-Fock Theory ................................................................................................. 21
3.1.4. Basis Set Approximation ........................................................................................... 22
3.1.5. Electron Correlation Methods ................................................................................... 22
3.2. Kinetic Theories ................................................................................................................ 28
3.2.1. MCRRKM – Theory and Implementation ................................................................ 28
3.3. Overcoming TST Limitations – MCRRKM Development ............................................... 33
3.3.1. Spin Forbidden Reactions ......................................................................................... 33
3.3.2. The 1D Hindered Rotor Approximation ................................................................... 36
3.3.3. Multi-well Reactions ................................................................................................. 40
3.3.4. Tunneling Effect ........................................................................................................ 42
3.3.5. Bimolecular Reactions .............................................................................................. 53
3.3.6. Variable Reaction Coordinate Transition State Theory – VRC-TST ........................ 54
4 Germane and Germylene Decomposition Kinetics ................................................................... 59
4.1. Introduction ....................................................................................................................... 59
4.2. Methodology ..................................................................................................................... 62
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4.3. Results and Discussion ..................................................................................................... 64
4.3.1. Ab initio Calculations and Evaluation of High-pressure Rate Constants ................. 64
4.3.2. GeH and GeH Decomposition Kinetics ................................................................. 70
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4.4. Conclusions ...................................................................................................................... 76
5 Toluene Decomposition: Secondary Chemistry ........................................................................ 77
5.1. Introduction ...................................................................................................................... 77
5.2. Computational Methodology ............................................................................................ 80
5.2.1. Electronic Structure Methods ................................................................................... 80
5.2.2. Kinetic Theories ....................................................................................................... 81
5.3. Fulvenallene Decomposition ............................................................................................ 82
5.3.1. Analysis of the Reactivity on the C H Potential Energy Surface ............................ 82
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5.3.2. Fulvenallene Decomposition Kinetics ...................................................................... 94
5.4. Benzyl Decomposition ................................................................................................... 101
5.5. Kinetic Simulations of Toluene and Benzyl Decomposition ......................................... 105
5.5.1. Kinetic Model ......................................................................................................... 105
5.5.2. Comparison with Experiments ............................................................................... 107
5.6. Concluding Remarks ...................................................................................................... 112
6 New Reaction Pathways Active in Cyclopentadiene Pyrolysis .............................................. 115
6.1. Introduction .................................................................................................................... 115
6.2. Computational Methodology .......................................................................................... 117
6.2.1. Electronic Structure Calculations ........................................................................... 117
6.2.2. RRKM/Master Equation Calculations .................................................................... 119
6.2.3. Kinetic Mechanism and Experimental Data Simulations ....................................... 121
6.3. Kinetics of the cC H + cC H Reaction ........................................................................ 121
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6.3.1. Analysis of the Potential Energy Surface ............................................................... 122
6.3.2. Master Equation Integration and Rate Constant Estimation .................................. 128
6.4. The Kinetics of the C H + C H Reaction ..................................................................... 131
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6.4.1. Analysis of the Potential Energy Surface ............................................................... 131
6.4.2. ME/RRKM Simulations ......................................................................................... 135
6.5. Comparisons between Model Predictions and Experimental Data................................. 137
6.5.1. Pyrolysis in Georgia Flow Reactor ......................................................................... 138
6.5.2. Pyrolysis and Oxidation Study in Princeton Flow Reactor .................................... 139
6.6. Concluding Remarks ...................................................................................................... 141
7 Quantum Tunneling in Hydrogen Transfer Reactions: A Study on the CH +H Reaction . 143
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7.1. Introduction .................................................................................................................... 143
7.2. Computational Methodology .......................................................................................... 146
7.3. Sensitivity Analyses ....................................................................................................... 147
7.3.1. Level of Ab initio Theory ....................................................................................... 148
7.3.2. Level of Approximation for IRC Calculations ....................................................... 154
7.4. Comparison with Experiments and Accurate Theories .................................................. 157
7.5. Concluding Remarks ...................................................................................................... 159

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