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Poul Jørgensen

Gauge-Origin Independent Formulation and Implementation of Magneto-Optical Activity within Atomic-Orbital-Density Based Hartree-Fock and Kohn-Sham Response Theories

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  • Thomas Kjærgaard, Danmark
  • Poul Jørgensen
  • Andreas Thorvaldsen, University of Tromsø, Norge
  • Pawel Salek, The Royal Institute of Technology, Polen
  • Sonia Coriani, Universita degli Studi di Trieste, Italien
  • Institut for Kemi
A Lagrangian approach has been used to derive gauge-origin independent expressions
for two properties that rationalize magneto-optical activity, namely the Verdet constant
V(ω) of the Faraday effect and the B term of magnetic circular dichroism. The approach is
expressed in terms of an atomic-orbital density-matrix based formulation of response theory
and use London atomic orbitals to parametrize the magnetic field dependence. It yields a
computational procedure which is both gauge-origin independent and suitable for linear-scaling
at the level of time-dependent Hartree-Fock and density functional theory. The formulation
includes a modified preconditioned conjugated gradient algorithm, which projects out the excited
state component from the solution to the linear response equation. This is required when solving
one of the response equations for the determination of the B term and divergence is encountered
if this component is not projected out. Illustrative results are reported for the Verdet constant of
H2, HF, CO, N2O, and CH3CH2CH3 and for the B term of pyrimidine, phosphabenzene, and
pyridine. The results are benchmarked against gauge-origin independent CCSD values.
OriginalsprogEngelsk
TidsskriftJournal of Chemical Theory and Computation
Vol/bind5
Sider (fra-til)1997–2020
Antal sider23
ISSN1549-9618
StatusUdgivet - 7 jun. 2009

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