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Polarization propagator calculations of the polarizability tensor at imaginary frequencies and long-range interactions for the noble gases and n-alkanes
Linköpings universitet, Institutionen för fysik, kemi och biologi, Beräkningsfysik. Linköpings universitet, Tekniska högskolan.
Linköpings universitet, Institutionen för fysik, kemi och biologi, Teoretisk Fysik. Linköpings universitet, Tekniska högskolan.
Linköpings universitet, Institutionen för fysik, kemi och biologi, Teoretisk Fysik. Linköpings universitet, Tekniska högskolan.ORCID-id: 0000-0002-6281-868X
2003 (engelsk)Inngår i: Journal of Chemical Physics, ISSN 0021-9606, Vol. 118, nr 20, s. 9167-9174Artikkel i tidsskrift (Fagfellevurdert) 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.

sted, utgiver, år, opplag, sider
2003. Vol. 118, nr 20, s. 9167-9174
HSV kategori
Identifikatorer
URN: urn:nbn:se:liu:diva-14047DOI: 10.1063/1.1568082OAI: oai:DiVA.org:liu-14047DiVA, id: diva2:22525
Tilgjengelig fra: 2006-10-05 Laget: 2006-10-05 Sist oppdatert: 2013-10-02
Inngår i avhandling
1. Long-range intermolecular dispersion forces and circular dichroism spectra from first-principles calculations
Åpne denne publikasjonen i ny fane eller vindu >>Long-range intermolecular dispersion forces and circular dichroism spectra from first-principles calculations
2007 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
Abstract [en]

This work presents first-principles calculations of long-range intermolecular dispersion energies between two atoms or molecules and of electronic circular dichroism spectra of chiral molecules. The former is expressed in terms of the C6 dipole-dipole dispersion coefficients Δε, and the latter is given in terms of the extinction coefficient. In a series of publications, the complex linear polarization propagator method has been shown to be a powerful tool to provide accurate ab initio and first-principles density functional theory results. This was the case not only for the C6 dispersion coefficients but also for the electronic circular dichroism at an arbitrary wavelength ranging from the optical to the X-ray regions of the spectrum. The selected samples for the investigation of dispersion interactions in the electronic ground state are the noble gases, n-alkanes, polyacenes, azabenzenes, alkali-metal clusters, and C60. It is found that the values of C6 for the sodium-cluster-to-fullerene interactions are well within the error bars of the experiment. 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 π → π* 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 π → π* excited state is smaller 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 which makes it possible to construct a simple structure-to-property relationship based on the number of π-bonds for the dispersion interaction in these saturated compounds. However, this simple approach is not applicable to the interactions of the π-conjugated systems since, depending on the systems, their characteristic frequencies ω1 can vary greatly. In addition, an accomplishment of calculations of the electronic circular dichroism spectra in the near-edge X-ray absorption has been demonstrated.

sted, utgiver, år, opplag, sider
Institutionen för fysik, kemi och biologi, 2007. s. 42
Serie
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1118
Emneord
van der Waals forces, dispersion forces, dispersion coefficients, polarizability, electronic circular dichroism
HSV kategori
Identifikatorer
urn:nbn:se:liu:diva-10151 (URN)978-91-85831-41-8 (ISBN)
Disputas
2007-10-02, Planck, Fysikhuset, Campus Valla, Linköping University, Linköping, 10:15 (engelsk)
Opponent
Veileder
Tilgjengelig fra: 2007-11-16 Laget: 2007-11-16 Sist oppdatert: 2020-03-24
2. First-principles calculations of long-range intermolecular dispersion forces
Åpne denne publikasjonen i ny fane eller vindu >>First-principles calculations of long-range intermolecular dispersion forces
2006 (engelsk)Licentiatavhandling, med artikler (Annet vitenskapelig)
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.

sted, utgiver, år, opplag, sider
Institutionen för fysik, kemi och biologi, 2006. s. 31
Serie
Linköping Studies in Science and Technology. Thesis, ISSN 0280-7971 ; 1217
Emneord
van der Waals forces, dispersion forces, intermolecular interactions, dispersion coefficients, polarizability
HSV kategori
Identifikatorer
urn:nbn:se:liu:diva-7512 (URN)9185457892 (ISBN)
Presentation
2006-01-16, Jordan-Fermi, Fysikhuset, Campus Valla, Linköpings universitet, Linköping, 14:00 (engelsk)
Opponent
Veileder
Merknad

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

Tilgjengelig fra: 2006-10-05 Laget: 2006-10-05 Sist oppdatert: 2020-04-01

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