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Title: Spectroscopic accuracy directly from quantum chemistry: Application to ground and excited states of beryllium dimer

We combine explicit correlation via the canonical transcorrelation approach with the density matrix renormalization group and initiator full configuration interaction quantum Monte Carlo methods to compute a near-exact beryllium dimer curve, without the use of composite methods. In particular, our direct density matrix renormalization group calculations produce a well-depth of D{sub e} = 931.2 cm{sup −1} which agrees very well with recent experimentally derived estimates D{sub e} = 929.7±2 cm{sup −1} [J. M. Merritt, V. E. Bondybey, and M. C. Heaven, Science 324, 1548 (2009)] and D{sub e}= 934.6 cm{sup −1} [K. Patkowski, V. Špirko, and K. Szalewicz, Science 326, 1382 (2009)], as well the best composite theoretical estimates, D{sub e} = 938±15 cm{sup −1} [K. Patkowski, R. Podeszwa, and K. Szalewicz, J. Phys. Chem. A 111, 12822 (2007)] and D{sub e}=935.1±10 cm{sup −1} [J. Koput, Phys. Chem. Chem. Phys. 13, 20311 (2011)]. Our results suggest possible inaccuracies in the functional form of the potential used at shorter bond lengths to fit the experimental data [J. M. Merritt, V. E. Bondybey, and M. C. Heaven, Science 324, 1548 (2009)]. With the density matrix renormalization group we also compute near-exact vertical excitation energies at the equilibrium geometry. These provide non-trivial benchmarksmore » for quantum chemical methods for excited states, and illustrate the surprisingly large error that remains for 1 {sup 1}Σ{sub g}{sup −} state with approximate multi-reference configuration interaction and equation-of-motion coupled cluster methods. Overall, we demonstrate that explicitly correlated density matrix renormalization group and initiator full configuration interaction quantum Monte Carlo methods allow us to fully converge to the basis set and correlation limit of the non-relativistic Schrödinger equation in small molecules.« less
Authors:
; ;  [1] ;  [2] ;  [3]
  1. Department of Chemistry, Frick Laboratory, Princeton University, New Jersey 08544 (United States)
  2. Department of Theoretical and Computational Molecular Science, Institute for Molecular Science, Okazaki, Aichi 444-8585 (Japan)
  3. Laboratory of Atomic and Solid State Physics, Cornell University, New York 14853 (United States)
Publication Date:
OSTI Identifier:
22253453
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 10; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ACCURACY; BERYLLIUM; BOND LENGTHS; CONFIGURATION INTERACTION; DENSITY MATRIX; DIMERS; EQUATIONS OF MOTION; EXCITATION; EXCITED STATES; MONTE CARLO METHOD; RENORMALIZATION