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Adsorption and diffusion in zeolites: A computational study
Vlugt, T.J.H.
Publication date
2000
Link to publication
Citation for published version (APA):
Vlugt, T. J. H. (2000). Adsorption and diffusion in zeolites: A computational study.
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Contents s
11 Introduction 1
1.11 Zeolites 1
1.22 Molecular Simulations 2
1.33 Scope of this thesis 6
22 Configurational-Bias Monte Carlo methods 7
2.11 Introduction 7
2.22 Dual cut-off CBMC 9
2.33 Parallel CBMC 11
2.3.11 Introduction 11
2.3.22 Algorithm 11
2.3.33 Discussion 14
2.3.44 Results and discussion 15
2.44 Generation of trial segments for branched molecules 18
2.55 Conclusions 22
2.66 Appendix A: Model details 22
2.77 Appendix B: Proof of equation 2.21 22
2.88 Appendix C: Alternative parallel algorithm 23
2.99 Appendix D: Growth of isobutane 24
33 Recoil growth algorithm for chain molecules with continuous interactions 25
3.11 Introduction 25
3.22 Description of the algorithm 26
3.2.11 Construction of a chain 26
3.2.22 Detailed balance condition and acceptance probability 27
3.2.33 Comparison with CBMC 29
3.33 Simulations 29
3.3.11 Simulation details 29
3.3.22 Efficiency of RG compared to CBMC 31
3.44 Conclusions 34
3.55 Appendix A: Alternative algorithm to compute the weight 34
3.66 Appendix B: Parallelization 37
3.77 Appendix C: Fixed endpoints 38
44 Adsorption of alkanes in Silicalite 41
4.11 Introduction 41
4.22 Model 42
4.33 Simulation technique 43
vii Contents
4.4.11 Heats of adsorption and Henry coefficients 44
4.4.22 Adsorption isotherms 45
4.4.33 Discussion 47 4.55 Branched alkanes 56 4.66 Fitting of simulated isotherms with dual-site Langmuir model 62
4.77 Conclusions 62 4.88 Appendix A: Alkane model 63
4.99 Appendix B: Discussion of the experimental data 64
4.9.11 Heats of adsorption 64 4.9.22 Henry coefficients 67 55 Adsorption of mixtures of alkanes in Silicalite 69
5.11 Introduction 69 5.22 Mixture Isotherms 69 5.33 Consequences for Diffusion 74
5.3.11 The Maxwell-Stefan theory for zeolite diffusion 74 5.3.22 Diffusion of a single component in Silicalite 75
5.3.33 Diffusion of binary mixtures 75
5.44 Conclusions 80
66 Diffusion of Isobutane in Silicalite studied by Transition Path Sampling 81
6.11 Introduction 81 6.22 Transition Path Sampling 82
6.2.11 Introduction 82 6.2.22 Monte Carlo sampling from the distribution F (xo,T) 84
6.2.33 Transition State Ensemble 86 6.2.44 Integrating the equations of motion 87
6.33 Simulation and model details 87
6.44 Results 89 6.4.11 Calculating the hopping rate 89
6.4.22 Transition state ensemble 91
6.55 Conclusions 93 6.66 Appendix A: Calculation of a free energy profile 93
6.77 Appendix B: Bitwise time-reversible multiple time-step algorithm 94
6.88 Appendix C: Parallel tempering 96
6.8.11 Introduction 96 6.8.22 Application to transition path sampling 97
6.8.33 Model system 97
Bibliographyy 101 Summaryy 109 Samenvattingg (Summary in Dutch) 113
Curriculumm Vitae 117 Publishedd work 119 Acknowledgementss 121
