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Tucker Carrington Jr

Publications and source records attributed to Tucker Carrington Jr.

6 recordsLinked to original sources

Efficiently transforming from values of a function on a sparse grid to basis coefficients

In many contexts it is necessary to determine coefficients of a basis expansion of a function ${f}\left(x_1, \ldots, x_D\right) $ from values of the function at points on a sparse grid. Knowing the coefficients, one has an interpolant or a surrogate. For example, such coefficients are used in uncertainty quantification. In this chapter, we present an efficient method for computing the coefficients. It uses basis functions that, like the familiar piecewise linear hierarchical functions, are zero at points in previous levels. They are linear combinations of any, e.g. global, nested basis functions $φ_{i_k}^{\left(k\right)}\left(x_k\right)$. Most importantly, the transformation from function values to basis coefficients is done, exploiting the nesting, by evaluating sums sequentially. When the number of functions in level $\ell_k$ equals $\ell_k$ (i.e. when the level index is increased by one, only one point (function) is added) and the basis function indices satisfy ${\left\lVert\mathbf{i}-\mathbf{1}\right\lVert_1 \le b}$, the cost of the transformation scales as $\mathcal{O}\left(D \left[\frac{b}{D+1} + 1\right] N_\mathrm{sparse}\right)$, where $N_\mathrm{sparse}$ is the number of points on the sparse grid. We compare the cost of doing the transformation with sequential sums to the cost of other methods in the literature.

math.NA↗

Machine learning optimization of the collocation point set for solving the Kohn-Sham equation

The rectangular collocation approach makes it possible to solve the Schrödinger equation with basis functions that do not have amplitude in all regions in which wavefunctions have significant amplitude. Collocation points can be restricted to a small region of space. As no integrals are computed, there are no problems due to discontinuities in the potential, and there is no need to use integrable basis functions. In this paper, we show, for the Kohn-Sham equation, that machine learning can be used to drastically reduce the size of the collocation point set. This is demonstrated by solving the Kohn-Sham equations for CO and H2O. We solve the Kohn-Sham equation on a given effective potential which is a critical part of all DFT calculations, and monitor orbital energies and orbital shapes. We use a combination of Gaussian process regression and a genetic algorithm to reduce the collocation point set size by more than an order of magnitude (from about 51,000 points to 2,000 points) while retaining mHartree accuracy.

physics.comp-ph↗

Using rectangular collocation with finite difference derivatives to solve electronic Schrodinger equation

We show that a rectangular collocation method, equivalent to evaluating all matrix elements with a quadrature-like scheme and using more points than basis functions, is an effective approach for solving the electronic Schrödinger equation (ESE). We test the ideas by computing several solutions of the ESE for the H atom and the H2+ cation and several solutions of a Kohn-Sham equation for CO and H2O. In all cases, we achieve millihartree accuracy. Two key advantages of the collocation method we use are: 1) collocation points need not have a particular distribution or spacing and can be chosen to reduce the required number of points; 2) the better the basis, is the less sensitive are the results to the choice of the point set. The ideas of this paper make it possible to use any basis functions and thus open to the door to using basis functions that are not Gaussians or plane waves. We use basis functions that are similar to Slater type orbitals. They are rarely used with the variational method, but present no problems when used with collocation.

physics.comp-ph↗

Infrared spectrum and intermolecular potential energy surface of the CO-O2 dimer

Only a few weakly-bound complexes containing the O2 molecule have been characterized by high resolution spectroscopy, no doubt due to the complications added by the oxygen molecule's unpaired electron spin. Here we report an extensive infrared spectrum of CO-O2, observed in the CO fundamental band region using a tunable quantum cascade laser to probe a pulsed supersonic jet expansion. The rotational energy level pattern derived from the spectrum consists of stacks of levels characterized by the total angular momentum, J, and its projection on the intermolecular axis, K. Five such stacks are observed in the ground vibrational state, and ten in the excited state (v(CO) = 1). They are divided into two groups, with no observed transitions between groups. The groups correspond to different projections of the O2 electron spin, and correlate with the two lowest rotational states of O2, (N, J) = (1, 0) and (1, 2). The rotational constant of the lowest K = 0 stack implies an effective intermolecular separation of 3.82 Angstroms, but this should be interpreted with caution since it ignores possible effects of electron spin. A new high-level 4-dimensional potential energy surface is developed for CO-O2, and rotational energy levels are calculated for this surface, ignoring electron spin. By comparing calculated and observed levels, it is possible to assign detailed quantum labels to the observed level stacks.

physics.atm-clus↗

The He2 - OCS complex: comparison between theory and experiment

OCS is an ideal probe for quantum solvation effects in cold helium clusters. He2-OCS is the "second step" in going from a single OCS molecule to a large doped superfluid helium cluster. Here assignment of the spectrum of He2-OCS is significantly extended to higher values of J, K, and vt (the low frequency torsional vibration). The observation of a new infrared band, OCS nu1 + nu3, taken together with the known nu1 band, enables assignments to be verified by comparing ground state combination differences. Relatively straightforward scaling of previously calculated theoretical energy levels gives a remarkably good fit to experiment

physics.atm-clus↗

Using symmetry-adapted optimized sum-of-products basis functions to calculate vibrational spectra

Vibrational spectra can be computed without storing full-dimensional vectors by using low-rank sum-of-products (SOP) basis functions. We introduce symmetry constraints in the SOP basis functions to make it possible to separately calculate states in different symmetry subgroups. This is done using a power method to compute eigenvalues and an alternating least squares method to optimize basis functions. Owing to the fact that the power method favours the convergence of the lowest states, one must be careful not to exclude basis functions of some symmetries. Exploiting symmetry facilitates making assignments and improves the accuracy. The method is applied to the acetonitrile molecule.

physics.chem-ph↗