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First-principles calculations of long-range intermolecular dispersion forces
Linköping University, Department of Physics, Chemistry and Biology, Theoretical Physics. Linköping University, The Institute of Technology.
2006 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

This work presents first-principles calculations of long-range intermolecular dispersion energies between two atoms or molecules as expressed in terms of the C6 dipole-dipole dispersion coefficients. In a series of publications, it has been shown by us that the complex linear polarization propagator method provides accurate ab initio and first-principles density functional theory values of the C6 dispersion coefficients in comparison with those reported in the literature. The selected samples for the investigation of dispersion interactions in the electronic ground state are the noble gases, n-alkanes, polyacenes, azabenzenes, and C60. It has been shown that the proposed method can also be used to determine dispersion energies for species in their respective excited electronic states. The C6 dispersion coefficients for the first ππ* excited state of the azabenzene molecules have been obtained with the adopted method in the multiconfiguration self-consistent field approximation. The dispersion energy of the ππ* excited state is smaller r than that of the ground state. It is found that the characteristic frequencies ω1 defined in the London approximation of n-alkanes vary in a narrow range and that makes it possible to construct a simple structure-to-property relation based on the number of -bonds for the dispersion interaction in these saturated compounds. However, this simple approach is not applicable for the interactions of the π-conjugated systems since their characteristic frequencies ω1 vary strongly depending on the systems.

Place, publisher, year, edition, pages
Institutionen för fysik, kemi och biologi , 2006. , 31 p.
Series
Linköping Studies in Science and Technology. Thesis, ISSN 0280-7971 ; 1217
Keyword [en]
van der Waals forces, dispersion forces, intermolecular interactions, dispersion coefficients, polarizability
National Category
Physical Sciences
Identifiers
URN: urn:nbn:se:liu:diva-7512ISBN: 9185457892 (print)OAI: oai:DiVA.org:liu-7512DiVA: diva2:22529
Presentation
2006-01-16, Jordan-Fermi, Fysikhuset, Campus Valla, Linköpings universitet, Linköping, 14:00 (English)
Opponent
Supervisors
Note

Report code: LIU-TEK-LIC-2006:2

Available from: 2006-10-05 Created: 2006-10-05 Last updated: 2017-12-08
List of papers
1. Polarization propagator calculations of the polarizability tensor at imaginary frequencies and long-range interactions for the noble gases and n-alkanes
Open this publication in new window or tab >>Polarization propagator calculations of the polarizability tensor at imaginary frequencies and long-range interactions for the noble gases and n-alkanes
2003 (English)In: Journal of Chemical Physics, ISSN 0021-9606, Vol. 118, no 20, 9167-9174 p.Article in journal (Refereed) Published
Abstract [en]

The linear polarization propagator has been computed at imaginary frequencies for He, Ne, Ar, and Kr as well as for the n-alkanes including heptane and its smaller members. It is shown that an effective and direct evaluation of the polarization propagator using standard electronic structure first principle methods can be achieved on the whole imaginary axis without expanding the polarizability in a series of the Cauchy moments. The linear response equation will be complex in this case, but an effective algorithm can be constructed so that the computational cost parallels that of the real propagator. Calculations of the polarizability tensor are used to determine the Casimir–Polder interaction potentials for the molecules under consideration. Theoretical results for the C6 dispersion coefficient are compared with accurate experimental data, and it is shown that results for the extended n-alkanes obtained with density functional theory and the hybrid B3LYP exchange correlation functional are in excellent agreement with experiment. At the same level of theory, on the other hand, there are significant discrepancies for the noble gas atoms. The electron correlation contribution to C6 is less than 9% for the n-alkanes and decreases with the size of the system.

National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-14047 (URN)10.1063/1.1568082 (DOI)
Available from: 2006-10-05 Created: 2006-10-05 Last updated: 2013-10-02
2. C6 dipole-dipole dispersion coefficients for the n-alkanes: Test of an additivity procedure
Open this publication in new window or tab >>C6 dipole-dipole dispersion coefficients for the n-alkanes: Test of an additivity procedure
2004 (English)In: Physical Review A, ISSN 1050-2947, Vol. 69, no 44701, 44701- p.Article in journal (Refereed) Published
Abstract [en]

We report on calculations of the dipole-dipole dispersion coefficients for pairs of n -alkane molecules. The results are based on first-principles calculations of the molecular polarizabilities with a purely imaginary frequency argument and which were reported by us in a previous work [P. Norman, A. Jiemchooroj, and Bo E. Sernelius, J. Chem. Phys. 118, 9167 (2003)]. The results for the static polarizabilities and dispersion coefficients are compared to simple algebraic expressions in terms of the number of CC and CH bonds in the two weakly interacting species. The bond additivity procedure is shown to perform well in the present case, and bond polarizabilities of 4.256 and 3.964  a.u . are proposed for the CH and the CC bond, respectively.

National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-14048 (URN)10.1103/PhysRevA.69.044701 (DOI)
Note
Original Publication: Auayporn Jiemchooroj, Bo E. Sernelius and Patrick Norman, C6 dipole-dipole dispersion coefficients for the n-alkanes: Test of an additivity procedure, 2004, Physical Review A, (69), 44701, 44701. http://dx.doi.org/10.1103/PhysRevA.69.044701 Copyright: American Physical Society http://www.aps.org/ Available from: 2006-10-05 Created: 2006-10-05 Last updated: 2013-10-02
3. First principle calculations of dipole-dipole dispersion coefficients for the ground and first pi π → π* excited states of some azabenzenes
Open this publication in new window or tab >>First principle calculations of dipole-dipole dispersion coefficients for the ground and first pi π → π* excited states of some azabenzenes
2004 (English)In: Journal of Computational Methods in Science and Engineering, Vol. 4, no 3, 321-332 p.Article in journal (Refereed) Published
Abstract [en]

The complex polarization propagator method has been applied to the calculation of dipole-dipole dispersion coefficients (also known as C_6 coefficients) of pyridine, pyrazine, and s-tetrazine. These calculations refer to the electronic ground states as well as the first excited states of π → π* character. It is argued that accurate ground state dispersion coefficients are obtained with density functional theory using the B3LYP exchange-correlation functional. The proposed values for the C_6 coefficients of pyridine, pyrazine, and s-tetrazine in their ground states are 1543 a.u., 1398 a.u., and 1014 a.u., respectively. Multi-configurational complete active space calculations are performed on these compounds in their respective π → π* excited state. The isotropic averages of the frequency-dependent polarizabilities are smaller in the excited states, but the effective frequencies - defined in the London - van der Waals dispersion relation - are on the other hand larger.

National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-14049 (URN)
Available from: 2006-10-05 Created: 2006-10-05 Last updated: 2013-10-02
4. Complex polarization propagator method for calculation of dispersion coefficients of extended π-conjugated systems: The C6 coefficients of polyacenes and C60
Open this publication in new window or tab >>Complex polarization propagator method for calculation of dispersion coefficients of extended π-conjugated systems: The C6 coefficients of polyacenes and C60
2005 (English)In: Journal of Chemical Physics, ISSN 0021-9606, Vol. 123, no 12, 124312- p.Article in journal (Refereed) Published
Abstract [en]

The frequency-dependent polarizabilities and the C6 dipole-dipole dispersion coefficients for the first members of the polyacenes namely benzene, naphthalene, anthracene, and naphthacene as well as the fullerene C60 have been calculated at the time-dependent Hartree-Fock level and the time-dependent density-functional theory level with the hybrid B3LYP exchange-correlation functional. The dynamic polarizabilities at imaginary frequencies are obtained with use of the complex linear polarization propagator method and the C6 coefficients are subsequently determined from the Casimir-Polder relation. We report the first ab initio calculations of the C6 coefficients for the molecules under consideration, and our recommended value for the dispersion coefficient of the fullerene is 101.0  a.u.

Keyword
organic compounds, fullerenes, atomic clusters, polarisability, HF calculations, density functional theory, ab initio calculations
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-14050 (URN)10.1063/1.2035589 (DOI)
Available from: 2006-10-05 Created: 2006-10-05 Last updated: 2013-10-02

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