The trust-region self-consistent field method: Towards a black-box optimization in Hartree–Fock and Kohn–Sham theories
The trust-region self-consistent field (TRSCF) method is presented for optimizing the total energy ESCF of Hartree–Fock theory and Kohn–Sham density-functional theory. In the TRSCF method, b...
The trust-region self-consistent field (TRSCF) method is presented for optimizing the total energy ESCF of Hartree–Fock theory and Kohn–Sham density-functional theory. In the TRSCF method, b...
All-forward semiclassical simulations of nonlinear response functions
We propose a quantum trajectory algorithm for computing nonlinear response functions of condensed phase molecular systems based on a time-ordered expansion of the density matrix. The nth-order respons...
We propose a quantum trajectory algorithm for computing nonlinear response functions of condensed phase molecular systems based on a time-ordered expansion of the density matrix. The nth-order respons...
Excitation energies from time-dependent density-functional theory beyond the adiabatic approximation
J. Chem. Phys. 121, 28 (2004); doi:10.1063/1.1756865
Issue Date: 1 July 2004
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Time-dependent density-functional theory in the adiabatic approximation has been very successful for calculating excitation energies in molecular systems. This paper studies nonadiabatic effects for excitation energies, using the current–density functional of Vignale and Kohn [Phys. Rev. Lett. 77, 2037 (1996)]. We derive a general analytic expression for nonadiabatic corrections to excitation energies of finite systems and calculate singlet s
s and sp excitations of closed-shell atoms. The approach works well for ss excitations, giving a small improvement over the adiabatic local-density approximation, but tends to overcorrect sp excitations. We find that the observed problems with the nonadiabatic correction have two main sources: (1) the currents associated with the sp excitations are highly nonuniform and, in particular, change direction between atomic shells, (2) the so-called exchange-correlation kernels of the homogeneous electron gas, f
and f
, are incompletely known, in particular in the high-density atomic core regions. ©2004 American Institute of Physics.
s and sp excitations of closed-shell atoms. The approach works well for ss excitations, giving a small improvement over the adiabatic local-density approximation, but tends to overcorrect sp excitations. We find that the observed problems with the nonadiabatic correction have two main sources: (1) the currents associated with the sp excitations are highly nonuniform and, in particular, change direction between atomic shells, (2) the so-called exchange-correlation kernels of the homogeneous electron gas, f| History: | Received 8 March 2004; accepted 8 April 2004 |
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