Journal of Chemical Physics
Feedback | Help | Exit
The Journal of Chemical Physics
Search:
   
 
 
 
Previous Article
Classical flux integrals in transition state theory: Generalized reaction coordinates
Transition state theory (TST) approximates the reactive flux in an elementary chemical reaction by the instantaneous flux passing through a hypersurface (the "transition state") which comple...
Next Article
Unitary group based open-shell coupled cluster theory: Application to van der Waals interactions of high-spin systems
The performance of the unitary group approach (UGA) based coupled cluster singles and doubles (CCSD) method in application to van der Waals interactions involving high-spin open-shell systems is exami...

Towards standard methods for benchmark quality ab initio thermochemistry—W1 and W2 theory

J. Chem. Phys. 111, 1843 (1999); doi:10.1063/1.479454

Issue Date: 1 August 1999

You are not logged in to this journal. Log in

Jan M. L. Martin and Glênisson de Oliveira
Department of Organic Chemistry, Kimmelman Building, Room 262, Weizmann Institute of Science, 76100 Rehovot, Israel
Two new schemes for computing molecular total atomization energies (TAEs) and/or heats of formation (Delta H<sub>f</sub><sup>[convolution]</sup>) of first- and second-row compounds to very high accuracy are presented. The more affordable scheme, W1 (Weizmann-1) theory, yields a mean absolute error of 0.30 kcal/mol and includes only a single, molecule-independent, empirical parameter. It requires CCSD (coupled cluster with all single and double substitutions) calculations in spdf and spdfg basis sets, while CCSD(T) (i.e., CCSD with a quasiperturbative treatment of connected triple excitations) calculations are only required in spd and spdf basis sets. On workstation computers and using conventional coupled cluster algorithms, systems as large as benzene can be treated, while larger systems are feasible using direct coupled cluster methods. The more rigorous scheme, W2 (Weizmann-2) theory, contains no empirical parameters at all and yields a mean absolute error of 0.23 kcal/mol, which is lowered to 0.18 kcal/mol for molecules dominated by dynamical correlation. It involves CCSD calculations in spdfg and spdfgh basis sets and CCSD(T) calculations in spdf and spdfg basis sets. On workstation computers, molecules with up to three heavy atoms can be treated using conventional coupled cluster algorithms, while larger systems can still be treated using a direct CCSD code. Both schemes include corrections for scalar relativistic effects, which are found to be vital for accurate results on second-row compounds. ©1999 American Institute of Physics.
History: Received 22 February 1999; accepted 3 May 1999
Permalink: http://link.aip.org/link/?JCPSA6/111/1843/1
BUY THIS ARTICLE   (US$24)
Download HTML Download Sectioned HTML Download PDF (132 kB) View Cart

KEYWORDS and PACS

Keywords
PACS
  • 31.15.Ar
    Electronic structure of atoms, molecules and their ions: theory Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) Ab initio calculations
  • 33.15.Fm
    Molecular properties and interactions with photons Properties of molecules and molecular ions Bond strengths, dissociation energies
  • 82.60.Cx
    Physical chemistry Chemical thermodynamics Enthalpies of combustion, reaction, and formation
  • 31.15.Dv
    Electronic structure of atoms, molecules and their ions: theory Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) Coupled cluster theory
  • 31.30.Jv
    Electronic structure of atoms, molecules and their ions: theory Corrections to electronic structure Relativistic and quantum electrodynamic effects in atoms and molecules
  • YEAR: 1999

PUBLICATION DATA

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

REFERENCES (75)
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. Computational Thermochemistry, edited by K. K. Irikura and D. J. Frurip, ACS Symposium Series, Nr. 677 (American Chemical Society, Washington, DC, 1998).
  2. L. A. Curtiss, K. Raghavachari, G. W. Trucks, and J. A. Pople, J. Chem. Phys. 94, 7221 (1991).
  3. L. A. Curtiss, K. Raghavachari, P. C. Redfern, V. Rassolov, and J. A. Pople, J. Chem. Phys. 109, 7764 (1998).
  4. J. A. Montgomery Jr., J. W. Ochterski, and G. A. Petersson, J. Chem. Phys. 101, 5900 (1994), and references therein.
  5. J. W. Ochterski, G. A. Petersson, and J. A. Montgomery Jr., J. Chem. Phys. 104, 2598 (1996).
  6. J. A. Montgomery, Jr., M. J. Frisch, J. W. Ochterski, and G. A. Petersson, J. Chem. Phys. 110, 2822 (1999).
  7. J. M. L. Martin, in Encyclopedia of Computational Chemistry (Wiley, New York, 1998), Vol. 5.
  8. J. M. L. Martin and P. R. Taylor, J. Phys. Chem. A 103, 4427 (1999).
  9. L. A. Curtiss, K. Raghavachari, P. C. Redfern, and J. A. Pople, J. Chem. Phys. 106, 1063 (1997).
  10. A. D. Becke, J. Comput. Chem. 20, 63 (1999), and references therein;
    11. see also A. D. Becke, J. Chem. Phys. 107, 8554 (1997);
    H. L. Schmider and A. D. Becke, 108, 9624 (1998);
    109, 8188 (1998).
  11. NIST-JANAF Thermochemical Tables, 4th ed., edited by M. W. Chase Jr., J. Phys. Chem. Ref. Data Monograph 9 (1998).
  12. J. D. Cox, D. D. Wagman, and V. A. Medvedev, CODATA Key Values for Thermodynamics (Hemisphere, New York, 1989).
  13. J. M. L. Martin, Chem. Phys. Lett. 259, 669 (1996).
  14. J. M. L. Martin and P. R. Taylor, J. Chem. Phys. 106, 8620 (1997).
  15. J. M. L. Martin, Chem. Phys. Lett. 242, 343 (1995).
  16. C. Schwartz in Methods in Computational Physics 2, edited by B. J. Alder (Academic, New York, 1963).
  17. R. N. Hill, J. Chem. Phys. 83, 1173 (1985).
  18. W. Kutzelnigg and J. D. Morgan III, J. Chem. Phys. 96, 4484 (1992);
    19. 97, 8821 (1992).
  19. J. M. L. Martin and P. R. Taylor, J. Phys. Chem. A 102, 2995 (1998).
  20. T. Helgaker, W. Klopper, H. Koch, and J. Noga, J. Chem. Phys. 106, 9639 (1997).
  21. C. W. Bauschlicher Jr. and A. Ricca, J. Phys. Chem. A 102, 8044 (1998).
  22. T. H. Dunning Jr., in Encyclopedia of Computational Chemistry (Wiley, New York, 1998), Vol. 5;
    23. see also D. Feller and K. A. Peterson, J. Chem. Phys. 108, 154 (1998).
  23. J. M. L. Martin, J. Chem. Phys. 108, 2791 (1998).
  24. C. W. Bauschlicher Jr. and H. Partridge, Chem. Phys. Lett. 240, 533 (1995).
  25. H.-J. Werner, and P. J. Knowles, MOLPRO 97.3, a package of ab initio programs, with contributions from J. Almlöf, R. D. Amos, A. Berning, D. L. Cooper, M. J. O. Deegan, A. J. Dobbyn, F. Eckert, S. T. Elbert, C. Hampel, R. Lindh, A. W. Lloyd, W. Meyer, A. Nicklass, K. A. Peterson, R. M. Pitzer, A. J. Stone, P. R. Taylor, M. E. Mura, P. Pulay, M. Schütz, H. Stoll, and T. Thorsteinsson.
  26. MOLPRO is a package of ab initio programs written by H.-J. Werner and P. J. Knowles, with contributions from J. Almlöf, R. D. Amos, A. Berning, D. L. Cooper, M. J. O. Deegan, A. J. Dobbyn, F. Eckert, S. T. Elbert, C. Hampel, R. Lindh, A. W. Lloyd, W. Meyer, A. Nicklass, K. Peterson, R. Pitzer, A. J. Stone, P. R. Taylor, M. E. Mura, P. Pulay, M. Schütz, H. Stoll, and T. Thorsteinsson.
  27. J. Noga and R. J. Bartlett, J. Chem. Phys. 86, 7041 (1987);
    28. 89, 3401 (1988).
  28. J. F. Stanton, J. Gauss, J. D. Watts, W. Lauderdale, and R. J. Bartlett (1996) ACES II, an ab initio program system, incorporating the MOLECULE vectorized molecular integral program by Almlöf, J., and Taylor, P. R., and a modified version of the ABACUS integral derivative package by T. Helgaker, H. J. Aa. Jensen, P. Jørgensen, J. Olsen, and P. R. Taylor.
  29. T. H. Dunning Jr., J. Chem. Phys. 90, 1007 (1989).
  30. D. E. Woon and T. H. Dunning Jr., J. Chem. Phys. 98, 1358 (1993).
  31. R. A. Kendall, T. H. Dunning, and R. J. Harrison, J. Chem. Phys. 96, 6796 (1992).
  32. G. D. Purvis III and R. J. Bartlett, J. Chem. Phys. 76, 1910 (1982).
  33. K. Raghavachari, G. W. Trucks, J. A. Pople, and M. Head-Gordon, Chem. Phys. Lett. 157, 479 (1989).
  34. J. D. Watts, J. Gauss, and R. J. Bartlett, J. Chem. Phys. 98, 8718 (1993).
  35. T. J. Lee and G. E. Scuseria, in Quantum Mechanical Electronic Structure Calculations with Chemical Accuracy, edited by S. R. Langhoff (Kluwer, Dordrecht, The Netherlands, 1995), pp. 47–108.
  36. D. E. Woon and T. H. Dunning Jr., J. Chem. Phys. 103, 4572 (1995).
  37. J. M. L. Martin and P. R. Taylor, Chem. Phys. Lett. 225, 473 (1994).
  38. R. J. Gdanitz and R. Ahlrichs, Chem. Phys. Lett. 143, 413 (1988).
  39. R. D. Cowan and M. Griffin, J. Opt. Soc. Am. 66, 1010 (1976).
  40. R. L. Martin, J. Phys. Chem. 87, 750 (1983).
  41. M. Douglas and N. M. Kroll, Ann. Phys. (N.Y.) 82, 89 (1974);
    42. R. Samzow, B. A. Heß, and G. Jansen, J. Chem. Phys. 96, 1227 (1992), and references therein.
  42. C. L. Collins and R. S. Grev J. Chem. Phys. 108, 5465 (1998).
  43. C. W. Bauschlicher Jr., Theor. Chem. Acc.101, 421 (1999).
  44. B. A. Heß, C. M. Marian, and S. D. Peyerimhoff, in Modern Electronic Structure Theory, Vol. 1, edited by D. R. Yarkony (World Scientific, Singapore, 1995), pp. 152–278.
  45. GAUSSIAN 98, Revision A.3, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. G. Johnson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, and J. A. Pople (Gaussian, Inc., Pittsburgh, PA, 1998).
  46. A. D. Becke, J. Chem. Phys. 98, 5648 (1993).
  47. C. Lee, W. Yang, and R. G. Parr, Phys. Rev. B 37, 785 (1988).
  48. J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Pederson, D. J. Singh, and C. Fiolhais, Phys. Rev. B 46, 6671 (1992), and references therein.
  49. J. M. L. Martin and O. Uzan, Chem. Phys. Lett. 282, 16 (1998).
  50. J. M. L. Martin, J. Phys. Chem. A 102, 1394 (1998).
  51. J. M. L. Martin, Spectrochim. Acta A 55, 713 (1999).
  52. J. M. L. Martin and P. R. Taylor, Mol. Phys. 96, 681 (1999).
  53. J. M. L. Martin, in Energetics of Stable Molecules and Reactive Intermediates, edited by M. E. Minas da Piedade, NATO ASI Series C 535 (Kluwer, Dordrecht, 1999), pp. 373–415.
  54. F. Jensen, J. Chem. Phys. (submitted).
  55. D. Feller, J. Chem. Phys. 96, 6104 (1992).
  56. A. Halkier, T. Helgaker, P. Jørgensen, W. Klopper, H. Koch, J. Olsen, and A. K. Wilson, Chem. Phys. Lett. 286, 243 (1998).
  57. R. J. Gdanitz, J. Chem. Phys. 110, 706 (1999).
  58. G. de Oliveira, J. M. L. Martin, F. De Proft, and P. Geerlings, Phys. Rev. A (in press).
  59. M. Scheer, R. C. Bilodeau, and H. K. Haugen, Phys. Rev. Lett. 80, 2562 (1998).
  60. D. Calabrese, A. M. Covington, and J. S. Thompson, Phys. Rev. A 54, 2797 (1996).
  61. M. Scheer, R. C. Bilodeau, J. Thogersen, and H. K. Haugen, Phys. Rev. A 57, R1493 (1998).
  62. J. Thogersen, L. D. Steele, M. Scheer, C. A. Brodie, and H. K. Haugen, J. Phys. B 29, 1323 (1996).
  63. K. A. Peterson, D. E. Woon, and T. H. Dunning Jr., J. Chem. Phys. 100, 7410 (1994).
  64. C. E. Moore, Atomic Energy Levels, Natl. Bur. Stand. (US) Circ. 1949, 467.
  65. R. D. Johnson III and J. F. Liebman, personal communication.
  66. T. J. Lee and P. R. Taylor, Int. J. Quantum Chem., Symp. 23, 199 (1989).
  67. J. M. L. Martin, J. El-Yazal, and J. P. François, J. Phys. Chem. 100, 15358 (1996).
  68. A. P. Scott and L. Radom, J. Phys. Chem. 100, 16 502 (1996).
  69. W. Klopper, J. Noga, H. Koch, and T. Helgaker, Theor. Chem. Acc. 97, 164 (1997).
  70. e.g. H. Koch, A. Sanchez de Meras, T. Helgaker, and O. Christiansen, J. Chem. Phys. 104, 4157 (1996).
  71. K. P. Huber and G. Herzberg, Constants of Diatomic Molecules (Van Nostrand Reinhold, New York, 1979).
  72. P. Geerlings, F. De Proft, and J. M. L. Martin, in Theoretical and Computational Chemistry, Vol. 4: Recent Developments and Applications of Modern Density Functional Theory, edited by J. Seminario (Elsevier, New York, 1996), p. 773.
  73. D. G. Truhlar, Chem. Phys. Lett. 294, 45 (1998).
  74. J. M. L. Martin, J. El-Yazal, and J. P. François, Mol. Phys. 86, 1437 (1995).
  75. H. Y. Afeefy, J. F. Liebman, and S. E. Stein, "Neutral Thermochemical Data" in NIST Chemistry WebBook, NIST Standard Reference Database Number 69, Eds. W. G. Mallard and P. J. Linstrom, November 1998, National Institute of Standards and Technology, Gaithersburg, MD, 20899 (http://webbook.nist.gov).

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