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A Polarization Propagator for Nonlinear X-ray Spectroscopies
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0002-1763-9383
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology. Linköping University, Sweden.ORCID iD: 0000-0002-1191-4954
2016 (English)In: Journal of Physical Chemistry Letters, ISSN 1948-7185, E-ISSN 1948-7185, Vol. 7, no 11, p. 1991-1995Article in journal (Refereed) Published
Resource type
Text
Abstract [en]

A complex polarization propagator approach has been developed to third order and implemented in density functional theory (DFT), allowing for the direct calculation of nonlinear molecular properties in the X-ray wavelength regime without explicitly addressing the excited-state manifold. We demonstrate the utility of this propagator method for the modeling of coherent near-edge X-ray two-photon absorption using, as an example, DFT as the underlying electronic structure model. Results are compared with the corresponding near edge X-ray absorption fine structure spectra, illuminating the differences in the role of symmetry, localization, and correlation between the two spectroscopies. The ramifications of this new technique for nonlinear X-ray research are briefly discussed.

Place, publisher, year, edition, pages
American Chemical Society , 2016. Vol. 7, no 11, p. 1991-1995
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-189373DOI: 10.1021/acs.jpclett.6b00750ISI: 000377239200009PubMedID: 27159130Scopus ID: 2-s2.0-84973568630OAI: oai:DiVA.org:kth-189373DiVA: diva2:947166
Note

QC 20160707

Available from: 2016-07-07 Created: 2016-07-04 Last updated: 2017-11-29Bibliographically approved
In thesis
1. Derivation and application of response functions for nonlinear absorption and dichroisms
Open this publication in new window or tab >>Derivation and application of response functions for nonlinear absorption and dichroisms
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is titled ’Derivation and application of response functions for nonlinear absorption and dichroisms’ and was written by Tobias Fahleson at the Division of Theoretical Chemistry & Biology at KTH Royal Institute of Technology in Sweden. It explores and expands upon theoretical means of quantifying a number of nonlinear spectroscopies, including two-photon absorption, resonant inelastic x-ray scattering, Jones birefringence, and magnetic circular dichroism. Details are provided for the derivation and program implementation of complex-valued (damped) cubic response functions that have been implemented in the quantum chemistry package DALTON [1], based on working equations formulated for an approximate-state wave function. This is followed by an assessment of the implementation. It is demonstrated how two-photon absorption (TPA) can be described either through second-order transition moments or the damped cubic response function. A set of illustrative TPA profiles are produced for smaller molecules. In addition, resonant inelastic x-ray scattering (RIXS) is explored in a similar manner as two-photon absorption. It is shown for small systems how RIXS spectra may be obtained using a reduced form of the cubic response function. Linear birefringences are investigated for noble gases, monosubstituted benzenes, furan homologues, and liquid acetonitrile. Regarding the noble gases, the Jones effect is shown to be proportional to a power series with respect to atomic radial sizes. For monosubstituted benzenes, a linear relation between the Jones birefringence and the empirical para-Hammett constant as well as the permanent electric dipole moment is presented. QM/MM protocols are applied for a pure acetonitrile liquid, including polarizable embedding and polarizable-density embedding models. The final chapter investigates magnetically induced circular dichroism (MCD). A question regarding relative stability of the first set of excited states for DNA-related molecular systems is resolved through MCD by exploiting the signed nature of circular dichroisms. Furthermore, to what extent solvent contributions affect MCD spectra and the effect on uracil MCD spectrum due to thionation is studied.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2018. p. 85
Series
TRITA-BIO-Report, ISSN 1654-2312 ; 2018:01
Keyword
Theoretical spectroscopy, cubic response theory, damped response theory, magnetic circular dichroism, linear birefringence, two-photon absorption, TPA, resonant-inelastic x-ray scattering, RIXS, DALTON program
National Category
Theoretical Chemistry
Research subject
Theoretical Chemistry and Biology
Identifiers
urn:nbn:se:kth:diva-218662 (URN)978-91-7729-627-0 (ISBN)
Public defence
2018-02-28, FA32, Roslagstullsbacken 21, Albanova, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Knut and Alice Wallenberg Foundation, KAW- 2013.0020Swedish Research Council, 621-2014-4646
Note

QC 20180108

Available from: 2018-01-08 Created: 2017-11-29 Last updated: 2018-01-08Bibliographically approved

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