Time-dependent Hartree-Fock random phase approximation

RPA, and CPHF. Time-dependent Hartree-Fock (TDFIF) is the Flartree-Fock approximation for the time-dependent Schrodinger equation. CPFIF stands for coupled perturbed Flartree-Fock. The random-phase approximation (RPA) is also an equivalent formulation. There have also been time-dependent MCSCF formulations using the time-dependent gauge invariant approach (TDGI) that is equivalent to multiconfiguration RPA. All of the time-dependent methods go to the static calculation results in the v = 0 limit. 

The simplest polarization propagator corresponds to choosing an HF reference and including only the h2 operator, known as the Random Phase Approximation (RPA). For the static case oj = 0) the resulting equations are identical to those obtained from a Time-Dependent Hartree-Fock (TDHF) analysis or Coupled Hartree-Fock approach, discussed in Section 10.5. 

Currently the time dependent DFT methods are becoming popular among the workers in the area of molecular modelling of TMCs. A comprehensive review of this area is recently given by renown workers in this field [116]. From this review one can clearly see [117] that the equations used for the density evolution in time are formally equivalent to those known in the time dependent Hartree-Fock (TDHF) theory [118-120] or in its equivalent - the random phase approximation (RPA) both well known for more than three quarters of a century (more recent references can be found in [36,121,122]). This allows to use the analysis performed for one of these equivalent theories to understand the features of others. 

The corrected Linear Response approach (cLR) consists in the use the TDDFT relaxed density and the corresponding apparent charges (7-38) into Eqs. (7-36) and (7-37) to obtain the first-order approximation to the state specific free energy of the excited state. The details of the implementation are described in Ref. [17], This corrected Linear Response computational scheme can be applied to the analogous of the Time Dependent Hartree-Fock approach either in the complete (Random Phase Approximation) or approximated (Tamm-Dancoff approximation or Cl singles, CIS) version. 

It has recently been shown [ 12] that time-dependent or linear-response theory based on local exchange and correlation potentials is inconsistent in the pure exchange limit with the time-dependent Hartree-Fock theory (TDHF) of Dirac [13] and with the random-phase approximation (RPA) [14] including exchange. The DFT-based exchange-response kernel [15] is inconsistent with the structure of the second-quantized Hamiltonian. 

Much more enigmatically, the first-order time-dependent self-consistent field approximation is also widely called the Random Phase Approximation (RPA). This terminology is entrenched and so, although the name time-dependent self-consistent perturbation theory is more descriptive and preferable to both time-dependent Hartree-Fock and RPA all are used more or less interchangeably. The evolution of the concept and phrase random phase approximation is sketched in Appendix 27.A to this chapter. 

The basic response equation of TDDFT has the same form as that of time-dependent Hartree-Fock theory, or of the Random Phase Approximation, i.e.,... 

For exact wave functions and those that fulfill the hyper-virial theorem by construction [e.g., time-dependent Hartree-Fock (TDFIF) or random phase approximation (RPA), TDDFT, see below] both forms are equivalent. Note that all virial theorems are exactly fulfilled only in a complete (i.e., usually infinitely large) AO basis. By a simultaneous computation of the transition dipole moments in the length and velocity forms and subsequent numerical... 

This approximation is better known as the time-dependent Hartree—Fock approximation (TDHF) (McLachlan and Ball, 1964) (see Section 11.1) or random phase approximation (RPA) (Rowe, 1968) and can also be derived as the linear response of an SCF wavefunction, as described in Section 11.2. Furthermore, the structure of the equations is the same as in time-dependent density functional theory (TD-DFT), although they differ in the expressions for the elements of the Hessian matrix E22. The polarization propagator in the RPA is then given as... 

At the SCF level all methods lead to the same expressions for the response functions as obtained in the random phase approximation, in Section 10.3, with the time-dependent Hartree-Fock approximation, in Chapter 11.1, or with SCF linear response theory. The QED and time-averaged QED method for an MCSCF energy was also shown to yield the same expressions as obtained from propagator or response theory in Sections 10.4 and 11.2. 

A simple application of the very general approach used in earlier sections leads to the time-dependent generalization of Hartree-Fock theory. The time-dependent Hartree-Fock (TDHF) equations (Dirac, 1929) were first formulated variationally by Frenkel (1934) they are also widely used in nuclear physics (see e.g. Thouless, 1%1) under the name random-phase approximation (RPA). Since the equations describe response to a perturbation, as in Section 11.9 but now time-dependent, they will... 

The relativistic or non-relativistic random-phase approximation (RRPA or RPA)t is a generalized self-consistent field procedure which may be derived making the Dirac/Hartree-Fock equations time-dependent. Therefore, the approach is often called time-dependent Dirac/Hartree-Fock. The name random phase comes from the original application of this method to very large systems where it was argued that terms due to interactions between many alternative pairs of excited particles, so-called two-particle-two-hole interactions ((2p-2h) see below) tend to... 

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