(Luận án tiến sĩ) nghiên cứu cấu trúc và tính thơm của một số cluster boron bằng phương pháp hóa học lượng tử

MINISTRY OF EDUCATION AND TRAINING QUY NHON UNIVERSITY DUONG VAN LONG A QUANTUM CHEMICAL RESEACH OF STRUCTURE AND AROMATICITY OF SOME BORON CLUSTERS DOCTORAL DISSERTATION: Theoretical and Physical Chemistry MINISTRY OF EDUCATION AND TRAINING QUY NHON UNIVERSITY DUONG VAN LONG A QUANTUM CHEMICAL RESEACH OF STRUCTURE AND AROMATICITY OF SOME BORON CLUSTERS Major: Theoretical and Physical Chemistry Code No: 9440119 Reviewer 1: Prof Dr Nguyen Ngoc Ha Reviewer 2: Prof Dr Tran Thai Hoa Reviewer 3: Prof Dr Duong Tuan Quang Supervisors: Assoc Prof Dr Nguyen Phi Hung Prof Dr Nguyen Minh Tho BINH DINH – 2023 DECLARATION This dissertation was written on the basis of research work carried out at Quy Nhon University, Binh Dinh province, under the supervision of Professor Nguyen Minh Tho and Associate Professor Nguyen Phi Hung I hereby declare that the results presented are original from my own research work Most of them were already published in peer-reviewed international journals For the use of the results from joint papers, I received permissions from my coauthors Quy Nhon Binh Dinh 06 November 2023 Author Duong Van Long ACKNOWLEDGEMENTS I would like to express my sincere gratitude to professors and colleagues at Quy Nhon University, my family and friends who have accompanied me throughout the long years of pursuing a doctoral program In particular, I would like to express sincere thanks to the professors and faculty staffs of the Department of Chemistry, Faculty of Natural Sciences and Postgraduate Training Office of Quy Nhon University for their support, understanding and for creating conditions for me to overcome obstacles caused by the COVID-19 pandemic I would like to express my deepest gratitude to my supervisors, Profs Nguyen Minh Tho and Nguyen Phi Hung, for their invaluable guidance and support throughout my academic journey Prof Tho and Prof Hung have been my scientific mentor since the beginning of my academic career, and I am truly grateful for their unwavering support and encouragement They provided me with the foundation and skills necessary to succeed in my academic pursuits Their expertise and mentorship have been instrumental in shaping my research and helping me achieve my academic goals I am honoured to have the opportunity to work under the guidance of both Professors Tho and Hung and I am forever grateful for their constant support Thank you, Nguyen Ngoc Tri, Phan Dang Cam Tu, My Phuong Pham Ho and Nguyen Minh Tam, for sharing and accompanying me on my academic path I would like to express my debt to my parents for their unconditional love and support Their guidance sacrifices and encouragement have been instrumental in shaping me into the person I am today Thank you, Mom and Dad, for everything I would also like to thank my wife and my little son for their love and encouragement My wife has been a constant source of inspiration and support She has stood by my side through thick and thin, even during long nights when she had/has to listen to the sound of clattering keyboards while I was, and I am, working on my academic projects I cannot thank her enough for her patience, understanding and foremost love And my little son, you are the driving force for me to move forward, to achieve what we have now and in the future I dedicate this thesis, my great achievement, to my family, and hope to continue making them proud Table of Contents List of symbols and notations List of Figures i iii ix List of Tables GENERAL INTRODUCTION A Research introduction B Objectives and scope of the research C Novelty and scientific significance Chapter DISSERTATION OVERVIEW 1.1 Overview of the research 1.2 Objectives of the research 1.3 Research content 1.4 Research methodology 1.4.1 Search for lower-lying isomers 1.4.2 ELF – The electron localization function 1.4.3 Ring current maps 1.4.4 Bond order and net atomic charge 10 Chapter THEORETICAL BACKGROUNDS COMPUTATIONAL METHODS 2.1 AND 11 Theoretical backgrounds of computational quantum chemistry 11 2.1.1 Schrödinger equation 11 2.1.2 The Born–Oppenheimer Approximation 11 2.1.3 Ab initio computational method 13 2.1.4 14 The Hartree-Fock Method 2.1.5 Density Functional Theory 15 2.1.6 Benchmarking the functional and basis set in DFT 19 2.1.7 Post-Hartree-Fock methods 21 2.2 Aromaticity models in boron clusters 24 2.2.1 The Hückel and Baird rules 24 2.2.2 Ribbon aromaticity 31 2.2.3 Disk aromaticity 40 2.2.4 Hollow cylinder model 46 Chapter RESULTS AND DISCUSSION 50 q 3.1 The Hückel rule and the ribbon model: The cases of B2Si3 and p B3Si2 clusters 50 3.1.1 Motivation for the study 50 3.1.2 The benchmarking tests 53 3.1.3 Ribbon aromaticity model versus the Hückel electron count 60 3.1.4 Concluding remarks 72 3.2 The disk aromaticity on the quasi-planar boron cluster B700/2- 73 3.2.1 Motivation of the study 74 3.2.2 The quasi-planar B700/2- 76 3.2.3 Disk model and electron count rule 78 3.2.4 Concluding remarks 82 3.3 Binary boron lithium clusters B12Lin with n = 1–14: the disk-cone model for the B12Li4 cluster 82 3.3.1 Motivation of the study 82 3.3.2 The growth pattern of B12Lin with n = – 14 84 3.3.3 Relative stabilities of clusters 3.3.4 Chemical Bonding 3.3.5 A mixed cone-disk model 3.3.6 Concluding remarks 10 3.4.B14FeLi2 and the hollow cylinder model 10 3.4.1 Motivation of the study 10 3.4.2 Stability of B14FeLi2 and its potential applications 10 3.4.3 Concluding remarks 11 Chapter GENERAL CONCLUSIONS AND FUTURE DIRECTIONS 112 4.1 General Conclusions 112 4.2 Future Directions 114 LIST OF PUBLICATIONS CONTRIBUTING TO THE DISSERTATION 116 REFERENCES 117 Appendix 133 List of symbols and notations 2D Two dimensional 3D Three dimensional ACID Anisotropy of the induced current density ADE Adiabatic detachment energy AdNDP Adaptive Natural Density Partitioning AO Atomic orbital ASBO Average of the sum of the bond orders CASSCF Complete Active Space Self-Consistent Field CBS Complete basis set CC Coupled cluster CCSD Coupled cluster including singles and doubles CCSD(T) CCSD with a perturbative triples correction CI Configuration Interaction CMO Canonical Molecular Orbital CTOCD-DZ2 Continuous transformation of the origin of the current density diamagnetic zero, with shifting the origin toward the nearest nucleus DFT Density functional theory DM Disk model DR Double ring ELF Electron localization function GA Genetic algorithm GGA Generalized gradient approximation GTO Gaussian-type orbitals HCM Hollow cylinder model HF Hartree-Fock HLG Frontier orbital (HOMO – LUMO) energy gap HOMO Highest Occupied Molecular Orbital i IEv IR-UV2CI LCAO Vertical ionization energy LDA Resonant infrared-ultraviolet two-color ionization spectroscopy LUMO Linear combination of atomic orbitals MBPT Local density approximation MEGA Lowest Unoccupied Molecular Orbital meta-GGA Many-body perturbation theory MO Mexican Enhanced Genetic Algorithm MPn Meta-generalized gradient approximation MRCI Molecular orbital NAC n-order Møller-Plesset perturbation method NICS Multireference Configuration Interaction PES Calculated net atomic charged PSM Nuclear independent chemical shift QP Photoelectron spectroscopy RMS Phenomenological shell model RSS Quasi-planar SBO Root mean square SOMO Residual sum of squares SPION Sum of bond orders STO Singly Occupied Molecular Orbital TD-DFT Superparamagnetic iron oxide nanoparticles TEAv Slater-type orbitals UV Time dependent density functional theory method UV-Vis Vertical two-electron affinity VASP Ultraviolet VDE Ultraviolet-Visible Vienna ab initio simulation package (VASP) Vertical detachment energy ii