Gaussian geminal basis set optimization with crude SCF reference state

Gaussian geminal basis functions for second-order correlation energy calculations according to the Sinanogˇlu method are optimized with reference to rather crude SCF functions. The optimized geminal basis set is then used in a one-step calculation of the correlation energy with respect to the near-Hartree-Fock reference State. The numerical results for the beryllium atom indicate the usefulness of the proposed technique.     

Non-Born-Oppenheimer study of positronic molecular systems: e(+)LiH

Very accurate non-Born-Oppenheimer variational calculations of the ground state of e(+)LiH have been performed using explicitly correlated Gaussian functions with preexponential factors dependent on powers of the internuclear distance. In order to determine the positron detachment energy of e(+)LiH and the dissociation energy corresponding to the e(+)LiH fragmentation into HPs and Li(+) we also calculated non-BO energies of HPs, LiH, and Li(+). For all the systems the calculations provided the lowest ever-reported variational upper-bounds to the ground state energies. Annihilation rates of HPs and e(+)LiH were also computed. The dissociation energy of e(+)LiH into HPs and Li(+) was determined to be 0.036 548 hartree.     

Fractional Brownian Motions and Enhanced Diffusion in a Unidirectional Wave-Like Turbulence

We study transport in random undirectional wave-like velocity fields with nonlinear dispersion relations. For this simple model, we have several interesting findings: (1) In the absence of molecular diffusion the entire family of fractional Brownian motions (FBMs), persistent or anti-persistent, can arise in the scaling limit. (2) The infrared cutoff may alter the scaling limit depending on whether the cutoff exceeds certain critical value or not. (3) Small, but nonzero, molecular diffusion can drastically change the scaling limit. As a result, some regimes stay intact; some (persistent) FBM regimes become non-Gaussian and some other FBM regimes become Brownian motions with enhanced diffusion coefficients. Moreover, in the particular regime where the scaling limit is a Brownian motion in the absence of molecular diffusion, the vanishing molecular diffusion limit of the enhanced diffusion coefficient is strictly larger than the diffusion coefficient with zero molecular diffusion. This is the first such example that we are aware of to demonstrate rigorously a nonperturbative effect of vanishing molecular diffusion on turbulent diffusion coefficient.     

From homogenization to averaging in cellular flows

We consider an elliptic eigenvalue problem with a fast cellular flow of amplitude A  , in a two-dimensional domain with L²$L^2$ cells. For fixed A  , and L→∞$L\to \infty$, the problem homogenizes, and has been well studied. Also well studied is the limit when L   is fixed, and A→∞$A\to \infty$. In this case the solution equilibrates along stream lines.     

Very accurate potential energy curve of the LiH molecule

We present very accurate calculations of the ground-state potential energy curve (PEC) of the LiH molecule performed with all-electron explicitly correlated Gaussian functions with shifted centers. The PEC is generated with the variational method involving simultaneous optimization of all Gaussians with an approach employing the analytical first derivatives of the energy with respect to the Gaussian nonlinear parameters (i.e., the exponents and the coordinates of the shifts). The LiH internuclear distance is varied between 1.8 and 40 bohrs. The absolute accuracy of the generated PEC is estimated as not exceeding 0.3 cm(-1). The adiabatic corrections for the four LiH isotopologues, i.e., (7)LiH, (6)LiH, (7)LiD, and (6)LiD, are also calculated and added to the LiH PEC. The aforementioned PECs are then used to calculate the vibrational energies for these systems. The maximum difference between the computed and the experimental vibrational transitions is smaller than 0.9 cm(-1). The contribution of the adiabatic correction to the dissociation energy of (7)LiH molecule is 10.7 cm(-1). The magnitude of this correction shows its importance in calculating the LiH spectroscopic constants. As the estimated contribution of the nonadiabatic and relativistic effects to the ground state dissociation energy is around 0.3 cm(-1), their inclusion in the LiH PEC calculation seems to be the next most important contribution to evaluate in order to improve the accuracy achieved in this work.     

Accurate variational calculations of the ground 2Po(1s22s22p) and excited 2S(1s22s2p2) and 2Po(1s22s23p) states of singly ionized carbon atom

In this article we report accurate nonrelativistic variational calculations of the ground and two excited states of C(+) ion. We employ extended and well optimized basis sets of all-electron explicitly correlated Gaussians to represent the wave functions of the states. The optimization of the basis functions is performed with a procedure employing the analytic gradient of the energy with respect to the nonlinear parameters of the Gaussians. The calculations explicitly include the effects due to the finite nuclear mass. The calculated transition energies between the three states are compared to the experimentally derived values. Finally, we present expectation values of some small positive and negative powers of the interparticle distances and contact densities.     

Extended floating spherical gaussian basis sets for molecules. Generation procedure and result for H2O

A procedure is proposed to generate extended floating spherical gaussian orbital (FSGO) basis sets for molecular SCF calculations by projecting large basis set SCF results onto FSGOs. This replaces the need for repeated evaluation of energy integrals and SCF iterations for extensive non-linear optimizations of FSGOs.     

N2-time-dependent SCF scheme

A new procedure for the Fock matrix operator construction is proposed. Its application for RHF calculations on diatomic molecules using Slater orbital basis sets shows that the computation time for the new SCF procedure is proportional to the square of the basis set size.     

Automated generation of coupled-cluster diagrams: implementation in the multireference state-specific coupled-cluster approach with the complete-active-space reference

An algorithm for generation of the spin-orbital diagrammatic representation, the corresponding algebraical formulas, and the computer code of the coupled-cluster (CC) method with an arbitrary level of the electronic excitations has been developed. The method was implemented in the general case as well as for specific application in the state-specific multireference coupled-cluster theory (SSMRCC) based on the concept of a "formal reference state." The algorithm was tested in SSMRCC calculations describing dissociation of a single bond and in calculations describing simultaneous dissociation of two single bonds--the problem requiring up to six-particle excitations in the CC operator.     

A(SLq(2)) at Roots of Unity is a Free Module over A(SL(2))

It is shown that when q is a primitive root of unity of order not equal to 2 mod 4, A(SL_q(2)) is a free module of finite rank over the coordinate ring of the classical group SL(2). An explicit set of generators is provided.