ORCID
https://orcid.org/0000-0002-0358-9274
Subject Area
Chemistry
Abstract
Noncovalent interactions (NCIs) and metal–ligand bonding contribute to structure, stability, and function in proteins, organometallic catalysts, and materials, yet they remain difficult to compare on a common quantitative scale. This dissertation implements Local Mode Analysis (LMA) as a framework for measuring interaction strengths via local force constants and derived bond strength orders, and for linking these metrics across chemically diverse systems.
First, a brief introduction on NCI types, myoglobin, artificial metalloproteins, and vibrational modes is discussed in Chapter 1, with the computational methods utilized in this dissertation outlined in Chapter 2. Then, in Chapter 3, the application of LMA in the context of group-II ansa-metallocenes clarifies how the bridging atom and metal center modulate metal–ring interactions and angle stiffness, rationalizing computed geometries and reactivity descriptors. In Chapter 4, analysis of forming/breaking-bond local force constants and stabilizing NCI’s (through LMA and energy decomposition analysis) in competing transition states explains enantioselectivity by identifying asymmetric strengthening of key hydrogen-bonding and pi-stacking contacts for alpha,beta amino acid derivatives formed under chiral Ir catalysis. Third, in Chapter 5, hybrid quantum mechanics/molecular mechanics (QM/MM) calculations on mutated myoglobin variants quantify how heme Fe–ligand local force constants and pi-pi interactions shift with sequence changes, yielding trends consistent with observed spectroscopic trends. In Chapter 6, QM/MM calculations on Schiff-Base myoglobin scaffolds revealed the effects of NCIs within the active pocket with different metals and small ligands. Lastly, in Chapter 7, the dissertation extends the application of LMA to porous framework materials using periodic density functional theory to characterize the interactions governing iodine (I2) capture in MOF-74.
Overall, the dissertation establishes procedures for using local force constants to interpret changes in bonding and NCIs and to relate these changes to computed or measured properties across the systems studied. Within the accuracy of the employed models, LMA-derived metrics align with observed trends in binding, selectivity, and framework stability and help prioritize hypotheses for further testing.
Degree Date
Summer 7-2-2026
Document Type
Dissertation
Degree Name
Ph.D.
Department
Chemistry
Advisor
Elfi Kraka
Second Advisor
Peng Tao
Third Advisor
Haoyuan Chen
Fourth Advisor
Lorena Tribe
Number of Pages
319
Format
Creative Commons License
This work is licensed under a Creative Commons Attribution-Noncommercial 4.0 License
Recommended Citation
Rodriguez Antonio, Juliana J., "Exploring Noncovalent Interactions: Insights From Gas Phase To QM/MM Metal Complexes Through Vibrational Spectroscopy" (2026). Chemistry Theses and Dissertations. 63.
https://scholar.smu.edu/hum_sci_chemistry_etds/63
