529-0003-00L  Advanced Quantum Chemistry

SemesterAutumn Semester 2016
LecturersM. Reiher, S. Knecht
Periodicityyearly recurring course
Language of instructionEnglish



Courses

NumberTitleHoursLecturers
529-0003-00 GAdvanced Quantum Chemistry
Lecture Tue 12:00-14:00, Exercise Classes Thursday 10:00-11:00
Vorlesung Di 12-14 Uhr, Uebung Donnerstag 10-11 Uhr
3 hrs
Tue12-14HCI J 4 »
Thu10-11HCI F 8 »
M. Reiher, S. Knecht

Catalogue data

AbstractAdvanced, but fundamental topics central to the understanding of theory in chemistry and for solving actual chemical problems with a computer.
Examples are:
* Operators derived from principles of relativistic quantum mechanics
* Relativistic effects + methods of relativistic quantum chemistry
* Open-shell molecules + spin-density functional theory
* New electron-correlation theories
ObjectiveThe aim of the course is to provide an in-depth knowledge of theory and method development in theoretical chemistry. It will be shown that this is necessary in order to be able to solve actual chemical problems on a computer with quantum chemical methods.

The relativistic re-derivation of all concepts known from (nonrelativistic) quantum mechanics and quantum-chemistry lectures will finally explain the form of all operators in the molecular Hamiltonian - usually postulated rather than deduced. From this, we derive operators needed for molecular spectroscopy (like those required by magnetic resonance spectroscopy). Implications of other assumptions in standard non-relativistic quantum chemistry shall be analyzed and understood, too. Examples are the Born-Oppenheimer approximation and the expansion of the electronic wave function in a set of pre-defined many-electron basis functions (Slater determinants). Overcoming these concepts, which are so natural to the theory of chemistry, will provide deeper insights into many-particle quantum mechanics. Also revisiting the workhorse of quantum chemistry, namely density functional theory, with an emphasis on open-shell electronic structures (radicals, transition-metal complexes) will contribute to this endeavor. It will be shown how these insights allow us to make more accurate predictions in chemistry in practice - at the frontier of research in theoretical chemistry.
Content1) Introductory lecture: basics of quantum mechanics and quantum chemistry
2) Einstein's special theory of relativity and the (classical) electromagnetic interaction of two charged particles
3) Klein-Gordon and Dirac equation; the Dirac hydrogen atom
4) Numerical methods based on the Dirac-Fock-Coulomb Hamiltonian, two-component and scalar relativistic Hamiltonians
5) Response theory and molecular properties, derivation of property operators, Breit-Pauli-Hamiltonian
6) Relativistic effects in chemistry and the emergence of spin
7) Spin in density functional theory
8) New electron-correlation theories: Tensor network and matrix product states, the density matrix renormalization group
9) Quantum chemistry without the Born-Oppenheimer approximation
Lecture notesA set of detailed lecture notes will be provided, which will cover the whole course.
Literature1) M. Reiher, A. Wolf, Relativistic Quantum Chemistry, Wiley-VCH, 2014, 2nd edition
2) F. Schwabl: Quantenmechanik für Fortgeschrittene (QM II), Springer-Verlag, 1997
[english version available: F. Schwabl, Advanced Quantum Mechanics]
3) R. McWeeny: Methods of Molecular Quantum Mechanics, Academic Press, 1992
4) C. R. Jacob, M. Reiher, Spin in Density-Functional Theory, Int. J. Quantum Chem. 112 (2012) 3661
http://onlinelibrary.wiley.com/doi/10.1002/qua.24309/abstract
5) K. H. Marti, M. Reiher, New Electron Correlation Theories for Transition Metal Chemistry, Phys. Chem. Chem. Phys. 13 (2011) 6750
http://pubs.rsc.org/en/Content/ArticleLanding/2011/CP/c0cp01883j
6) K.H. Marti, M. Reiher, The Density Matrix Renormalization Group Algorithm in Quantum Chemistry, Z. Phys. Chem. 224 (2010) 583
http://www.oldenbourg-link.com/doi/abs/10.1524/zpch.2010.6125
7) E. Mátyus, J. Hutter, U. Müller-Herold, M. Reiher, On the emergence of molecular structure, Phys. Rev. A 83 2011, 052512
http://pra.aps.org/abstract/PRA/v83/i5/e052512

Note also the standard textbooks:
A) A. Szabo, N.S. Ostlund. Verlag, Dover Publications
B) I. N. Levine, Quantum Chemistry, Pearson
C) T. Helgaker, P. Jorgensen, J. Olsen: Molecular Electronic-Structure Theory, Wiley, 2000
D) R.G. Parr, W. Yang: Density-Functional Theory of Atoms and Molecules, Oxford University Press, 1994
E) R.M. Dreizler, E.K.U. Gross: Density Functional Theory, Springer-Verlag, 1990
Prerequisites / NoticeStrongly recommended (preparatory) courses are: quantum mechanics and quantum chemistry

Performance assessment

Performance assessment information (valid until the course unit is held again)
Performance assessment as a semester course
ECTS credits7 credits
ExaminersM. Reiher, S. Knecht
Typesession examination
Language of examinationEnglish
RepetitionThe performance assessment is offered every session. Repetition possible without re-enrolling for the course unit.
Mode of examinationoral 30 minutes
This information can be updated until the beginning of the semester; information on the examination timetable is binding.

Learning materials

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Only public learning materials are listed.

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Offered in

ProgrammeSectionType
Chemistry MasterComputational ChemistryWInformation
Mathematics MasterQuantum ChemistryWInformation
Computational Science and Engineering BachelorAdditional Electives from the Fields of Specialization (CSE Master)WInformation
Computational Science and Engineering MasterChemistryWInformation