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Resonant-convergent second-order nonlinear response functions at the levels of Hartree-Fock and Kohn-Sham density functional theory
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
2017 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 147, no 14, article id 144109Article in journal (Refereed) Published
Abstract [en]

The second-order nonlinear (or cubic) response function is derived from the Ehrenfest theorem with inclusion made of the finite lifetimes of the excited states, representing the extension of the derivation of the quadratic response function in the same framework [P. Norman et al., J. Chem. Phys. 123, 194103 (2005)]. The resulting damped response functions are physically sound and converging also in near-resonance and resonance regions of the spectrum. Being an accurate approximation for small complex frequencies (defined as the sum of an optical frequency and an imaginary damping parameter), the polynomial expansion of the complex cubic response function in terms of the said frequencies is presented and used to validate the program implementation. In terms of approximate state theory, the computationally tractable expressions of the damped cubic response function are derived and implemented at the levels of Hartree-Fock and Kohn-Sham density functional theory. Numerical examples are provided in terms of studies of the intensity-dependent refractive index of para-nitroaniline and the two-photon absorption cross section of neon. For the latter property, a numerical comparison is made against calculations of the square of two-photon matrix elements that are identified from a residue analysis of the resonance-divergent quadratic response function.

Place, publisher, year, edition, pages
American Institute of Physics (AIP), 2017. Vol. 147, no 14, article id 144109
National Category
Theoretical Chemistry Other Physics Topics
Identifiers
URN: urn:nbn:se:kth:diva-217190DOI: 10.1063/1.4991616ISI: 000413201100012PubMedID: 29031277Scopus ID: 2-s2.0-85031678376OAI: oai:DiVA.org:kth-217190DiVA, id: diva2:1154636
Funder
Knut and Alice Wallenberg Foundation, KAW-2013.0020Swedish Research Council, 621-2014-4646
Note

QC 20171103

Available from: 2017-11-03 Created: 2017-11-03 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
Keywords
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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