Journal of Chemical Physics, Vol.121, No.13, 6145-6154, 2004
Quadratic response functions in the time-dependent four-component Hartree-Fock approximation
The second-order response function has been implemented in the time-dependent four-component Hartree-Fock approximation. The implementation is atomic orbital direct and formulated in terms of Fock-type matrices. It employs a quaternion symmetry scheme that provides maximum computational efficiency with consideration made to time-reversal and spatial symmetries. Calculations are presented for the electric dipole first-order hyperpolarizabilities of CsAg and CsAu in the second-harmonic generation optical process beta(-2omega;omega,omega). It is shown that relativistic corrections to property values are substantial in these cases-the orientationally averaged hyperpolarizabilities in the static limit (β) over bar (0;0,0) are overestimated in nonrelativistic calculations by 18% and 66% for CsAg and CsAu, respectively. The dispersion displays anomalies in the band gap region due to one- and two-photon resonances with nonrelativistically spin-forbidden states. Although weakly absorbing these states inflict divergences in the quadratic response function, since the response theoretical approach which is used adopts the infinite excited-state lifetime approximation. This fact calls for caution in applications where knowledge of the exact positioning of all excited states in the spectrum is unknown. (C) 2004 American Institute of Physics.