Symplectic integration and physical interpretation of time-dependent coupled-cluster theory

The formulation of the time-dependent Schrodinger equation in terms of coupled-cluster theory is outlined, with emphasis on the bivariational framework and its classical Hamiltonian structure. An indefinite inner product is introduced, inducing physical interpretation of coupled-cluster states in the form of transition probabilities, autocorrelation functions, and explicitly real values for observables, solving interpretation issues which are present in time-dependent coupled-cluster theory and in ground-state calculations of molecular systems under influence of external magnetic fields. The problem of the numerical integration of the equations of motion is considered, and a critial evaluation of the standard fourth-order Runge--Kutta scheme and the symplectic Gauss integrator of variable order is given, including several illustrative numerical experiments. While the Gauss integrator is stable even for laser pulses well above the perturbation limit, our experiments indicate that a system-dependent upper limit exists for the external field strengths. Above this limit, time-dependent coupled-cluster calculations become very challenging numerically, even in the full configuration interaction limit. The source of these numerical instabilities is shown to be rapid increases of the amplitudes as ultrashort high-intensity laser pulses pump the system out of the ground state into states that are virtually orthogonal to the static Hartree-Fock reference determinant.Comment: 14 pages, 13 figure

Model of optical response of marine aerosols to Forbush decreases

In order to elucidate the effect of galactic cosmic rays on cloud formation, we investigate the optical response of marine aerosols to Forbush decreases – abrupt decreases in galactic cosmic rays – by means of modeling. We vary the nucleation rate of new aerosols, in a sectional coagulation and condensation model, according to changes in ionization by the Forbush decrease. From the resulting size distribution we then calculate the aerosol optical thickness and Angstrom exponent, for the wavelength pairs 350, 450 nm and 550, 900 nm. In the cases where the output parameters from the model seem to compare best with atmospheric observations we observe, for the shorter wavelength pair, a change in Angstrom exponent, following the Forbush Decrease, of −6 to +3%. In some cases we also observe a delay in the change of Angstrom exponent, compared to the maximum of the Forbush decrease, which is caused by different sensitivities of the probing wavelengths to changes in aerosol number concentration and size. For the long wavelengths these changes are generally smaller. The types and magnitude of change is investigated for a suite of nucleation rates, condensable gas production rates, and aerosol loss rates. Furthermore we compare the model output with observations of 5 of the largest Forbush decreases after year 2000. For the 350, 450 nm pair we use AERONET data and find a comparable change in signal while the Angstrom Exponent is lower in the model than in the data, due to AERONET being mainly sampled over land. For 550, 900 nm we compare with both AERONET and MODIS and find little to no response in both model and observations. In summary our study shows that the optical properties of aerosols show a distinct response to Forbush Decreases, assuming that the nucleation of fresh aerosols is driven by ions. Shorter wavelengths seem more favorable for observing these effects and great care should be taken when analyzing observations, in order to avoid the signal being drowned out by noise

Polarizability and optical rotation calculated from the approximate coupled cluster singles and doubles CC2 linear response theory using Cholesky decompositions

A new implementation of the approximate coupled cluster singles and doubles CC2 linear response model using Cholesky decomposition of the two-electron integrals is presented. Significantly reducing storage demands and computational effort without sacrificing accuracy compared to the conventional model, the algorithm is well suited for large-scale applications. Extensive basis set convergence studies are presented for the static and frequency-dependent electric dipole polarizability of benzene and C60, and for the optical rotation of CNOFH2 and (−)-trans-cyclooctene (TCO). The origin-dependence of the optical rotation is calculated and shown to persist for CC2 even at basis set [email protected]

Reduced scaling in electronic structure calculations using Cholesky decompositions

We demonstrate that substantial computational savings are attainable in electronic structure calculations using a Cholesky decomposition of the two-electron integral matrix. In most cases, the computational effort involved calculating the Cholesky decomposition is less than the construction of one Fock matrix using a direct O(N2) [email protected]

Theoretical absorption spectrum of the Ar–CO van der Waals complex

The three-dimensional intermolecular electric dipole moment surface of Ar–CO is calculated at the coupled cluster singles and doubles level of theory with the aug-cc-pVTZ basis set extended with a 3s3p2d1f1g set of midbond functions. Using the rovibrational energies and wave functions of our recent study [J. Chem. Phys. 117, 6562 (2002)], temperature-dependent spectral intensities are evaluated and compared to available experimental data. Based on the theoretical spectrum, alternative assignments of the experimentally observed lines in the fundamental band of CO around 2160 and 2166 cm−1 are [email protected]