Articles you may be interested inPerformance of the antisymmetrized product of strongly orthogonal geminal (APSG) ansatz in describing ground states of molecules has been extensively explored in the recent years. Not much is known, however, about possibilities of obtaining excitation energies from methods that would rely on the APSG ansatz. In the paper we investigate the recently proposed extended random phase approximations, ERPA and ERPA2, that employ APSG reduced density matrices. We also propose a time-dependent linear response APSG method (TD-APSG). Its relation to the recently proposed phase including natural orbital theory is elucidated. The methods are applied to Li 2 , BH, H 2 O, and CH 2 O molecules at equilibrium geometries and in the dissociating limits. It is shown that ERPA2 and TD-APSG perform better in describing double excitations than ERPA due to inclusion of the so-called diagonal double elements. Analysis of the potential energy curves of Li 2 , BH, and H 2 O reveals that ERPA2 and TD-APSG describe correctly excitation energies of dissociating molecules if orbitals involved in breaking bonds are involved. For single excitations of molecules at equilibrium geometries the accuracy of the APSG-based methods approaches that of the time-dependent Hartree-Fock method with the increase of the system size. A possibility of improving the accuracy of the TD-APSG method for single excitations by splitting the electron-electron interaction operator into the long-and short-range terms and employing density functionals to treat the latter is presented.

We propose a method for calculating Coulomb matrix elements between exciton and biexciton states in semiconductor nanocrystals based on the envelope function formalism. We show that such a calculation requires proper treatment of the Bloch parts of the carrier wave functions which, in the leading order, leads to spin selection rules identical to those holding for optical interband transitions. Compared to the usual (intraband) Coulomb couplings, the resulting matrix elements are additionally scaled by the ratio of the lattice constant to the nanocrystal radius. As a result, the Coulomb coupling between exciton and biexciton states scale as 1/R 2 . We present also some statistical estimates of the distribution of the coupling magnitudes and energies of the coupled states The number of biexciton states coupled to exciton states form a certain energy range shows a power-law scaling with the ratio of the coupling magnitude to the energy separation. We estimate also the degree of mixing between exciton and biexciton states. The amount of biexciton admixture to exciton states at least 1 eV above the multiple exciton generation threshold can reach 80% but varies strongly with the nanocrystal size.

We present an electron-pairs-based method employing a generalized valence bond perfect-pairing (GVB-PP) ansatz providing a uniformly accurate description of systems where various types of electron correlation play a role and the GVB-PP wavefunction is a suitable reference. In the proposed EERPA-GVB approach a GVB-PP energy is amended by adding electron-pairs correlation. The latter is achieved by embedding single pairs, or couples of pairs, in the environment of the other electron fragments and separately accounting for intra-and inter-fragment correlation effects. For this purpose, we employ truncated extended random phase approximation equations. Application of EERPA-GVB to systems governed by both short-(energy barriers) and long-range (molecular interactions) correlation effects has proven good accuracy of 1