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Molecular Quadratic Response Properties with Inclusion of Relativity
Linköping University, Department of Physics, Chemistry and Biology, Computational Physics . Linköping University, The Institute of Technology.
2008 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis concerns quadratic response properties and their application to properties in Jablonski diagrams such as resonant two-photon absorption and excited state absorption. Our main interest lies in optical power limiting applications, and in this context, molecules containing heavy metal atoms prove superior. Therefore, we are interested in how relativity affects these properties, and in order to assess this, a four-component relativistic framework is adopted.

To properly address the molecular properties of interest, both relativistic effects and electron correlation need to be accounted for. These two properties are not additive, and, therefore, correlation needs to be incorporated into the four-component framework. We present the implementation of quadratic response properties at the four-component density functional level of theory. For second-harmonic generation, we have, with numerical examples, demonstrated that correlation and relativity are indeed not additive and that the inclusion of noncollinear magnetization is of little importance. We report that both electron correlation as well as relativity strongly affect results for second-harmonic generation. For example, relativity alone reduces the µβ-response signal by 62% and 75% for meta- and ortho-bromobenzene, respectively, and enhances the same response by 17% and 21% for meta- and ortho-iodobenzene, respectively.

In the four-component framework, we present the implementations of single and double residues of the quadratic response function, which allows for the evaluation of resonant two-photon absorption cross sections and excited state properties. Using these tools, we discuss different levels of approximation to the relativistic Hamiltonian and we demonstrate that for two-photon absorption, a proper treatment of relativistic effects qualitatively alters the spectrum. For example, already for an element as light as neon, significant differences are seen between the relativistic and nonrelativistic spectra as triplet transitions acquire substantial absorption cross sections in the former case.

Finally, quantum mechanics in conjunction with electrodynamics is applied to determine clamping levels in macroscopic samples. The microscopic properties of the optically active chromophores are determined by response theory, and then, electrodynamics is used to describe the interactions between the chromophores and incident laser pulses. Using this approach a series of molecules have been investigated and their performances have been compared and ranked in order to find novel materials for optical power limiting applications.

Place, publisher, year, edition, pages
Institutionen för fysik, kemi och biologi , 2008. , 36 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1167
Keyword [en]
relativistic quantum chemistry, molecular physics, clamping levels, four-component Hartree-Fock theory, Kohn-Sham density functional theory, response theory, nonlinear optics, second-harmonic generation, two-photon absorption, excited state properties, optical power limiting
National Category
Other Physics Topics
Identifiers
URN: urn:nbn:se:liu:diva-11035ISBN: 978-91-7393-957-7 (print)OAI: oai:DiVA.org:liu-11035DiVA: diva2:17492
Public defence
2008-04-11, Planck, Hus E, Campus Valla, Linköping University, Linköping, 10:15 (English)
Opponent
Supervisors
Available from: 2008-03-05 Created: 2008-03-05 Last updated: 2009-04-29
List of papers
1. Quadratic response functions in the relativistic four-component Kohn-Sham approximation
Open this publication in new window or tab >>Quadratic response functions in the relativistic four-component Kohn-Sham approximation
2008 (English)In: The Journal of Chemical Physics, ISSN 0021-9606, Vol. 128, no 2, 024105- p.Article in journal (Refereed) Published
Abstract [en]

A formulation and implementation of the quadratic response function in the adiabatic four-component Kohn-Sham approximation is presented. The noninteracting reference state is time-reversal symmetric and formed from Kramers pair spinors, and the energy density is gradient corrected. Example calculations are presented for the optical properties of disubstituted halobenzenes in their meta and ortho conformations. It is demonstrated that correlation and relativistic effects are not additive, and it is shown that relativity alone reduces the µ-response signal by 62% and 75% for meta- and ortho-bromobenzene, respectively, and enhances the same response by 17% and 21% for meta- and ortho-iodobenzene, respectively. Of the employed functionals, CAM-B3LYP shows the best performance and gives hyperpolarizabilities distinctly different from B3LYP

Keyword
density functional theory, eigenvalues and eigenfunctions, organic compounds, polarisability
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-12937 (URN)10.1063/1.2816709 (DOI)
Available from: 2008-03-05 Created: 2008-03-05 Last updated: 2009-04-29
2. Role of noncollinear magnetization for the first-order electric-dipole hyperpolarizability at the four-component
Open this publication in new window or tab >>Role of noncollinear magnetization for the first-order electric-dipole hyperpolarizability at the four-component
Manuscript (Other academic)
Identifiers
urn:nbn:se:liu:diva-12938 (URN)
Available from: 2008-03-05 Created: 2008-03-05 Last updated: 2010-01-13
3. Two-photon absorption in the relativistic four-component Hartree-Fock approximation
Open this publication in new window or tab >>Two-photon absorption in the relativistic four-component Hartree-Fock approximation
2005 (English)In: The Journal of Chemical Physics, ISSN 0021-9606, Vol. 122, no 11, 114106- p.Article in journal (Refereed) Published
Abstract [en]

A first implementation of the single residue of the quadratic response function in the four-component Hartree–Fock approximation is presented. The implementation is based on a Kramers paired molecular orbital basis and takes full advantage of time and spatial symmetry reductions in a quaternion formulation—in analogy with the previous work on the quadratic response function [J. Chem. Phys. 121, 6145 (2004)]. Sample calculations are given in terms of the monochromatic and coherent two-photon absorption cross sections in the noble gases. The relativistic two-photon selection rule J={0,±2} allows for nonrelativistically spin-forbidden transitions, and, even in neon, strong two-photon absorption is shown to occur for the X  1S02  3P2 transition. It is argued that relevant comparisons between nonrelativistic and relativistic calculations must be performed at the level of integrated absorption cross sections.

Keyword
two-photon processes, absorption, HF calculations, neon
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-13998 (URN)10.1063/1.1869469 (DOI)
Available from: 2006-10-05 Created: 2006-10-05
4. First order excited state properties in the four-component Hartree-Fock approximation; the excited state electric dipole moments in CsAg and CsAu
Open this publication in new window or tab >>First order excited state properties in the four-component Hartree-Fock approximation; the excited state electric dipole moments in CsAg and CsAu
2007 (English)In: The Journal of Chemical Physics, ISSN 0021-9606, Vol. 126, no 6, 064313- p.Article in journal (Refereed) Published
Abstract [en]

An implementation of the second-order residue of the quadratic response function is presented in the four-component Hartree-Fock approximation, and the calculation of first-order properties of electronically excited states can thereby be achieved. Results are presented for the excited state electric dipole moments of the valence excited states in CsAg and CsAu. For CsAg, and even more so for CsAu, nonscalar relativistic effects on this property may be substantial, e.g., at the four-component level of theory, the excited-to-ground state dipole moment difference µ ranges from 1.994  to  4.110  a.u. for the six components of the 1  3 state in CsAg, whereas, at the scalar relativistic level of theory, the common value of µ is 2.494  a.u.

National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-12940 (URN)10.1063/1.2436877 (DOI)
Available from: 2008-03-05 Created: 2008-03-05 Last updated: 2009-05-15
5. On the evaluation of quadratic response functions at the four-component Hartree-Fock level: Nonlinear polarization and two-photon absorption in bromo- and iodobenzen
Open this publication in new window or tab >>On the evaluation of quadratic response functions at the four-component Hartree-Fock level: Nonlinear polarization and two-photon absorption in bromo- and iodobenzen
2006 (English)In: The Journal of Chemical Physics, ISSN 0021-9606, Vol. 124, no 21, 214311- p.Article in journal (Refereed) Published
Abstract [en]

The nonlinear polarization and two-photon absorption parameters have been determined for dibromo- and di-iodobenzene in their meta- and ortho-conformations and with relativistic effects accounted for to a varying degree. By exclusion of small component integrals in the calculations of the first-order hyperpolarizability, results within 1% of fully relativistic four-component Hartree-Fock values are obtained at a cost of 8.7 times the corresponding nonrelativistic calculations. It is shown that the nonlinear absorption in bromobenzene (and even more so in iodobenzene) is broad banded due to spin-orbit interactions among the excited states, and nonrelativistic and scalar relativistic calculations are not to be used in this case.

Keyword
organic compounds, HF calculations, two-photon processes, relativistic corrections, polarisability, spin-orbit interactions, excited states
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-13999 (URN)10.1063/1.2204604 (DOI)
Available from: 2006-10-05 Created: 2006-10-05 Last updated: 2009-05-18
6. Theoretical Simulations of Clamping Levels in Optical Power Limiting
Open this publication in new window or tab >>Theoretical Simulations of Clamping Levels in Optical Power Limiting
2006 (English)In: Journal of Physical Chemistry B, ISSN 1520-5215, Vol. 110, no 42, 20912-20916 p.Article in journal (Refereed) Published
Abstract [en]

Multiphysics modeling, combining quantum mechanical and classical wave mechanical theories, of clamping levels has been performed for a platinum(II) organic compound in a sol−gel glass matrix. A clamping level of 2.5 μJ is found for a pulse duration of 10 ns. The excited-state absorption in the triplet manifold is shown to be crucial for clamping to occur.

National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-14001 (URN)10.1021/jp064167b (DOI)
Available from: 2006-10-05 Created: 2006-10-05

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