Theoretical investigations on cluster formation in mass spectrometry / vorgelegt von Alexander Haack. Wuppertal, März 2020
Content
1 Motivation
2 Introduction to Computational Chemistry
2.1 Electronic Structure Calculations
2.2 Nuclear Position and Movement
2.3 Thermochemistry
2.4 Reaction Dynamics
2.5 Collision Cross Section Modeling
3 Charge Retention/Charge Depletion in ESI-MS
3.1 Abstract
3.2 Introduction
3.3 Methods
3.4 Results and Discussion
3.4.1 Structure and Thermochemistry of the Different Clusters
3.4.2 Proton Transfer Paths
3.4.3 Multiply Charged Analytes
3.5 Conclusion
3.6 Supporting Information
3.7 Follow-up work
4 Modeling of Differential Ion Mobility
4.1 Abstract
4.2 Introduction
4.2.1 Mobility at low field strength
4.2.2 Mobility at high field strength
4.2.3 Differential Mobility Spectrometry
4.3 Computational Methods
4.3.1 Ab initio calculations
4.3.2 CCS calculations
4.3.3 Mobility calculations
4.3.4 Boltzmann weighting
4.3.5 Dispersion Plot calculation
4.4 Results and Discussion
4.4.1 Cluster structures
4.4.2 CCS fits: MD vs. rigid samples
4.4.3 Mobility calculations
4.4.4 Dispersion plots
4.5 Conclusion
4.6 Supporting Information
4.7 Follow-up work
5 Thermochemistry from MD Simulations
5.1 Abstract
5.2 Introduction
5.3 Theory and Methods
5.3.1 The quasiharmonic approximation (QHA)
5.3.2 Implementation and special considerations
5.3.3 Electronic structure and MD simulations
5.4 Results and Discussion
5.5 Summary and Conclusions
5.6 Appendix A - The Eckart Frame
5.7 Appendix B - Separating out Internal Rotation
5.8 Supporting Information
6 Summary and Outlook
6.1 Answering Questions from Experiment
6.2 Developing new Calculation Methods
6.3 General Conclusion
References