Role of noncollinear magnetization for the first-order electric-dipole hyperpolarizability at the four-component Kohn-Sham density functional theory level

• The quadratic response function has been derived and implemented at the adiabatic four-component Kohn-Sham density functional theory level with inclusion of noncollinear spin magnetization and gradient corrections in the exchange-correlation functional-a work that is an extension of our previous report where magnetization dependencies in the exchange-correlation functional were ignored [J. Henriksson, T. Saue, and P. Norman, J. Chem. Phys. 128, 024105 (2008)]. The electric-field induced second-harmonic generation experiments on CF3 Cl and CF3 Br are addressed by a determination of Β- (-2ω;ω,ω) for a wavelength of 694.3 nm, and the same property is also determined for CF3 I. The relativistic effects on the static hyperpolarizability for the series of molecules amount to 1%, 5%, and 9%, respectively. At the experimental wavelength, the contributions to Β due to the magnetization dependence in the exchange-correlation functional are negligible for CF3 Cl and CF3 Br and small for CF 3 I. The noticeable effect of magnetization in the latter case is attributed to a near two-photon resonance with the excited state 1 E3 (nonrelativistic notation). It is emphasized, however, that the effect of magnetization on Β for CF3 I is negligible both in comparison to the total relativistic correction as well as to the effects of electron correlation. It is concluded that, in calculations of hyperpolarizabilities under nonresonant conditions, the magnetization dependence in the exchange-correlation functional may be ignored. © 2009 American Institute of Physics.

Subject headings

NATURVETENSKAP  -- Kemi -- Teoretisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)

Keyword

Band structure

Correlation methods

Harmonic generation

Magnetization

Magnets

Programming theory

Hyper-polarizability

Kohn-Sham (KS) density

Magnetization dependence

Non resonant

Noncollinear magnetization

Photon resonance

Response functions

Spin magnetization

Density functional theory

NATURAL SCIENCES

Publication and Content Type

ref (subject category)

art (subject category)