Machine Learning Configuration Interaction

We propose the concept of machine learning configuration interaction (MLCI) whereby an artificial neural network is trained on-the-fly to predict important new configurations in an iterative selected configuration interaction procedure. We demonstrate that the neural network can discriminate between important and unimportant configurations, that it has not been trained on, much better than by chance. MLCI is then used to find compact wavefunctions for carbon monoxide at both stretched and equilibrium geometries. We also consider the multireference problem of the water molecule with elongated bonds. Results are contrasted with those from other ways of selecting configurations: first-order perturbation, random selection and Monte Carlo configuration interaction. Compared with these other serial calculations, this prototype MLCI is competitive in its accuracy, converges in significantly fewer iterations than the stochastic approaches, and requires less time for the higher-accuracy computations.Comment: This document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in The Journal of Chemical Theory and Computation, copyright American Chemical Society after peer review. To access the final edited and published work see https://pubs.acs.org/articlesonrequest/AOR-dANIFXJKzRAyR99E6hb

Characterizing a configuration interaction excited state using natural transition geminals

We introduce natural transition geminals as a means to qualitatively understand a transition where double excitations are important. The first two $A_{1}$ singlet states of the CH cation are used as an initial example. We calculate these states with configuration interaction singles (CIS) and state-averaged Monte Carlo configuration interaction (SA-MCCI). For each method we compare the important natural transition geminals with the dominant natural transition orbitals. We then compare SA-MCCI and full configuration interaction (FCI) with regards to the natural transition geminals using the beryllium atom. We compare using the natural transition geminals with analyzing the important configurations in the CI expansion to give the dominant transition for the beryllium atom and the carbon dimer. Finally we calculate the natural transition geminals for two electronic excitations of formamide.Comment: 15 pages, 2 figures. Mol. Phys. (2013

Approaching exact hyperpolarizabilities via sum-over-states Monte Carlo configuration interaction

We propose using sum-over-states calculations with the compact wavefunctions of Monte Carlo configuration interaction to approach accurate values for higher-order dipole properties up to second hyperpolarizabilities in a controlled way. We apply the approach to small systems that can generally be compared with full configuration interaction (FCI) results. We consider hydrogen fluoride with a 6-31g basis and then look at results, including frequency dependent properties, in an aug-cc-pVDZ basis. We extend one calculation beyond FCI by using an aug-cc-pVTZ basis. The properties of an H$_{4}$ molecule with multireference character are calculated in an aug-cc-pVDZ basis. We then investigate this method on a strongly multireference system with a larger FCI space by modelling the properties of carbon monoxide with a stretched geometry. The behavior of the approach with increasing basis size is considered by calculating results for the neon atom using aug-cc-pVDZ to aug-cc-pVQZ. We finally test if the unusual change in polarizability between the first two states of molecular oxygen can be reproduced by this method in a 6-31g basis.Comment: 11 pages, 14 figure

Exact and LDA entanglement of tailored densities in an interacting one-dimensional electron system

We calculate the `exact' potential corresponding to a one-dimensional interacting system of two electrons with a specific, tailored density. We use one-dimensional density-functional theory with a local-density approximation (LDA) on the same system and calculate densities and energies, which are compared with the `exact' ones. The `interacting-LDA system' corresponding to the LDA density is then found and its potential compared with the original one. Finally we calculate and compare the spatial entanglement of the electronic systems corresponding to the interacting-LDA and original interacting system.Comment: 7 pages, 4 figure

Applying Monte Carlo configuration interaction to transition metal dimers: exploring the balance between static and dynamic correlation

We calculate potential curves for transition metal dimers using Monte Carlo configuration interaction (MCCI). These results, and their associated spectroscopic values, are compared with experimental and computational studies. The multireference nature of the MCCI wavefunction is quantified and we estimate the important orbitals. We initially consider the ground state of the chromium dimer. Next we calculate potential curves for Sc$_{2}$ where we contrast the lowest triplet and quintet states. We look at the molybdenum dimer where we compare non-relativistic results with the partial inclusion of relativistic effects via effective core potentials, and report results for scandium nickel.Comment: 9 pages and 8 figure

Calculations of Potential Energy Surfaces Using Monte Carlo Configuration Interaction

We apply the method of Monte Carlo configuration interaction (MCCI) to calculate ground-state potential energy curves for a range of small molecules and compare the results with full configuration interaction. We show that the MCCI potential energy curve can be calculated to relatively good accuracy, as quantified using the non-parallelity error, using only a very small fraction of the FCI space. In most cases the potential curve is of better accuracy than its constituent single-point energies. We finally test the MCCI program on systems with basis sets beyond full configuration interaction: a lattice of fifty hydrogen atoms and ethylene. The results for ethylene agree fairly well with other computational work while for the lattice of fifty hydrogens we find that the fraction of the full configuration interaction space we were able to consider appears to be too small as, although some qualitative features are reproduced, the potential curve is less accurate.Comment: 14 pages, 22 figure

The SMC X-ray transient XTE J0111.2-7317 : a Be/X-ray binary in a SNR?

We report observations which confirm the identity of the optical/IR counterpart to the Rossi X-ray Timing Explorer transient source XTE J0111.2-7317. The counterpart is suggested to be a B0-B2 star (luminosity class III--V) showing an IR excess and strong Balmer emission lines. The distance derived from reddening and systemic velocity measurements puts the source in the SMC. Unusually, the source exhibits an extended asymetric H alpha structure.Comment: 5 pages, 3 figs, accepted by MNRA

Monte Carlo configuration interaction applied to multipole moments, ionisation energies and electron affinities

The method of Monte Carlo configuration interaction (MCCI) [1,2] is applied to the calculation of multipole moments. We look at the ground and excited state dipole moments in carbon monoxide. We then consider the dipole of NO, the quadrupole of the nitrogen molecule and of BH. An octupole of methane is also calculated. We consider experimental geometries and also stretched bonds. We show that these non-variational quantities may be found to relatively good accuracy when compared with FCI results, yet using only a small fraction of the full configuration interaction space. MCCI results in the aug-cc-pVDZ basis are seen to generally have reasonably good agreement with experiment. We also investigate the performance of MCCI when applied to ionisation energies and electron affinities of atoms in an aug-cc-pVQZ basis. We compare the MCCI results with full configuration-interaction quantum Monte Carlo [3,4] and `exact' non-relativistic results [3,4]. We show that MCCI could be a useful alternative for the calculation of atomic ionisation energies however electron affinities appear much more challenging for MCCI. Due to the small magnitude of the electron affinities their percentage errors can be high, but with regards to absolute errors MCCI performs similarly for ionisation energies and electron affinities.Comment: 12 pages, 20 figure

The Be/X-ray Transient V0332+53: Evidence for a tilt between the orbit and the equatorial plane?

We present optical and infrared observations of BQ Cam, the optical counterpart to the Be/X-ray transient system V0332+53. BQ Cam is shown to be an O8-9Ve star, which places V0332+53 at a distance of ~7 kpc. H-alpha spectroscopy and infrared photometry are used to discuss the evolution of the circumstellar envelope. Due to the low inclination of the system, parameters are strongly constrained. We find strong evidence for a tilt of the orbital plane with respect to the circumstellar disc (pressumably on the equatorial plane). Even though the periastron distance is only ~ 10 R_*, during the present quiescent state the circumstellar disc does not extend to the distance of periastron passage. Under these conditions, X-ray emission is effectively prevented by centrifugal inhibition of accretion. The circumstellar disc is shown to be optically dense at optical and infrared wavelengths, which together with its small size, is taken as an indication of tidal truncation.Comment: 9 pages, 3 figures, uses mn.sty and epsfig Accepted for publication in MNRA