Journal of Chemical Physics
Feedback | Help | Exit
The Journal of Chemical Physics
   
 
 
 
Previous Article
Application of magnetically perturbed time-dependent density functional theory to magnetic circular dichroism. II. Calculation of [script A] terms
The magnetically perturbed time-dependent density functional theory is used to derive equations for the magnetic circular dichroism (MCD) of degenerate transitions of closed shell molecules. The MCD o...
Next Article
Generalized-gradient exchange-correlation hole obtained from a correlation factor ansatz
The Perdew–Burke–Ernzerhof (PBE) approximation to the exchange-correlation energy is employed as reference point for the construction of an angle-averaged exchange-correlation hole. First,...

Parametric two-electron reduced-density-matrix method applied to computing molecular energies and properties at nonequilibrium geometries

J. Chem. Phys. 128, 234103 (2008); doi:10.1063/1.2937454

Published 19 June 2008

You are not logged in to this journal. Log in

A. Eugene DePrince, III, Eugene Kamarchik, and David A. Mazziotti
Department of Chemistry and The James Franck Institute, The University of Chicago, Chicago, Illinois 60637, USA
A parametric approach to the variational calculation of the two-electron reduced density matrix (2-RDM) for many-electron atoms and molecules has recently been developed in which the 2-RDM is parametrized to be both size consistent and nearly N-representable [C. Kollmar, J. Chem. Phys. 125, 084108 (2006); A. E. DePrince and D. A. Mazziotti, Phys. Rev. A 76, 049903 (2007)]. The parametric variational 2-RDM method is applied to computing ground-state molecular energies and properties at nonequilibrium geometries in significantly larger basis sets than previously employed. We study hydrogen abstraction from the hydroxide groups of H2O, NH3OH, and CH3OH. The 2-RDM method, parametrized by single and double excitations, shows significant improvement over coupled-cluster methods with similar excitations in predicting the shape of potential energy curves and bond-dissociation energies. Previous work completes the parametrization of the energy and 2-RDM by a system of n2h2 normalization constraints, where n and h are the number of occupied and unoccupied orbitals, respectively. In the present paper, however, we show that the constraints can be eliminated by incorporating them into the energy and 2-RDM functions and, hence, the constrained optimization of the ground-state energy can be reformulated as an unconstrained optimization. The 2-RDMs from the parametric method are very nearly N-representable, and as measured by an l2 norm, they are more accurate than the 2-RDMs from configuration interaction truncated at single and double excitations by an order of magnitude. ©2008 American Institute of Physics
History: Received 27 February 2008; accepted 6 May 2008; published 19 June 2008
Permalink: http://link.aip.org/link/?JCPSA6/128/234103/1
BUY THIS ARTICLE   (US$28)
Download HTML Download Sectioned HTML Download PDF (132 kB) View Cart

KEYWORDS and PACS

Keywords
PACS
  • 31.15.xt
    Variational techniques in atomic and molecular physics
  • 31.50.Bc
    Potential energy surfaces for ground electronic states (atoms and molecules)
  • 33.15.Fm
    Molecular bond strengths, dissociation energies
  • YEAR: 2008

RELATED DATABASES


To view database links for this article,
you need to log in.
To view database links for this article,
you need to log in.

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (38)
View in Separate Window/Tab
For access to fully linked references, you need to log in. For access to fully linked references, you need to Log in.
  1. F. Jensen, Introduction to Computational Chemistry, 2nd ed. (Wiley, New York, 2007);
  2. T. Helgaker, P. Jorgensen, and J. Olsen, Molecular Electronic-Structure Theory (Wiley, New York, 2000);
  3. A. Szabo and N. S. Ostlund, Modern Quantum Chemistry: Introduction to Advanced Electronic Structure Theory (Dover, New York, 1996).
  4. Two-electron Reduced-Density-Matrix Mechanics with Application to Many electron Atoms and Molecules, Advances in Chemical Physics Vol. 134, edited by D. A. Mazziotti (Wiley, New York, 2007).
  5. C. Garrod, V. Mihailović, and M. Rosina, J. Math. Phys. 10, 1855 (1975).
  6. R. M. Erdahl and B. Jin, in Many-Electron Densities and Density Matrices, edited by J. Cioslowski (Kluwer, Boston, 2000).
  7. D. A. Mazziotti and R. M. Erdahl, Phys. Rev. A 63, 042113 (2001).
  8. M. Nakata, H. Nakatsuji, M. Ehara, M. Fukuda, K. Nakata, and K. Fujisawa, J. Chem. Phys. 114, 8282 (2001).
  9. D. A. Mazziotti, Phys. Rev. A 65, 062511 (2002).
  10. Z. Zhao, B. J. Braams, H. Fukuda, M. L. Overton, and J. K. Percus, J. Chem. Phys. 120, 2095 (2004).
  11. D. A. Mazziotti, Phys. Rev. Lett. 93, 213001 (2004).
  12. G. Gidofalvi and D. A. Mazziotti, J. Chem. Phys. 122, 094107 (2005).
  13. E. Cancès, G. Stoltz, and M. Lewin, J. Chem. Phys. 125, 064101 (2006).
  14. D. A. Mazziotti, Acc. Chem. Res. 39, 207 (2006).
  15. D. A. Mazziotti, Phys. Rev. A 74, 032501 (2006).
  16. G. Gidofalvi and D. A. Mazziotti, J. Chem. Phys. 126, 024105 (2007).
  17. D. A. Mazziotti (unpublished).
  18. A. J. Coleman, Rev. Mod. Phys. 35, 668 (1962).
  19. C. Garrod and J. Percus, J. Math. Phys. 5, 1756 (1964).
  20. A. J. Coleman and V. I. Yukalov, Reduced Density Matrices: Coulson's Challenge (Springer-Verlag, New York, 2000).
  21. C. Kollmar, J. Chem. Phys. 125, 084108 (2006).
  22. A. E. DePrince and D. A. Mazziotti, Phys. Rev. A 76, 049903 (2007).
  23. R. Ahlrichs, P. Scharf, and C. Ehrhardt, J. Chem. Phys. 82, 890 (1985).
  24. D. A. Mazziotti, Phys. Rev. Lett. 97, 143002 (2006).
  25. D. A. Mazziotti, Phys. Rev. A 75, 022505 (2007);
    26. 76, 052502 (2007).
  26. D. A. Mazziotti, J. Chem. Phys. 126, 184101 (2007).
  27. C. Valdemoro, L. M. Tel, D. R. Alcoba, and E. Perez-Romero, Theor. Chem. Acc. 118, 503509 (2007).
  28. D. A. Mazziotti, J. Phys. Chem. A 111, 12635 (2007).
  29. F. Colmenero and C. Valdemoro, Phys. Rev. A 47, 979 (1993);
    30. H. Nakatsuji and K. Yasuda, Phys. Rev. Lett. 76, 1039 (1996);
    D. A. Mazziotti, Phys. Rev. A 57, 4219 (1998).
  30. R. Ahlrichs, Comput. Phys. Commun. 17, 31 (1979).
  31. L. Brillouin, J. Phys. (Paris), Colloq. 3, 373 (1932).
  32. J. M. Steele, The Cauchy-Schwarz Master Class: An Introduction to the Art of Mathematical Inequalities (Cambridge University Press, Cambridge, 2004).
  33. A. Wächter and L. T. Biegler, Math. Program. 106, 25 (2006).
  34. D. C. Liu and J. Nocedal, Math. Program. 45, 503 (1989).
  35. T. H. Dunning, Jr., J. Chem. Phys. 90, 1007 (1989).
  36. T. H. Dunning, Jr. and P. J. Hay, in Methods of Electronic Structure Theory, edited by H. F. Schaefer, III (Plenum, New York, 1977), Vol. 2.
  37. P. Piecuch, S. A. Kucharski, K. Kowalski, and M. Musial, Comput. Phys. Commun. 149, 71 (2002).
  38. M. W. Schmidt, K. K. Bladridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. Su, T. L. Windus, M. Dupuis, and J. A. Montgomery, Jr., J. Comput. Chem. 14, 1347 (1993).
  39. T. D. Crawford, C. D. Sherrill, E. F. Valeev, J. T. Fermann, R. A. King, M. L. Leininger, S. T. Brown, C. L. Janssen, E. T. Seidl, J. P. Kenny, and W. D. Allen, J. Comput. Chem. 28, 1610 (2007).
  40. Computational Chemistry Comparison and Benchmark Database, http://srdata. nist.gov/cccbdb

CITING ARTICLES
For access to citing articles, you need to log in.
For access to citing articles, you need to Log in.


Copyright © American Institute of Physics