Skip to main content
SpringerLink
Log in

Chemical accuracy in ab initio thermochemistry and spectroscopy: current strategies and future challenges

  • Regular Article
  • Published:
Theoretical Chemistry Accounts Aims and scope Submit manuscript

Abstract

The current state of the art in wavefunction-based electronic structure methods is illustrated via discussions of the most important effects incorporated into a selection of high-accuracy methods chosen from the chemical literature. If one starts with a high-quality correlation treatment, such as provided by the CCSD(T) coupled cluster method, the leading effects include convergence of the results with respect to the 1-particle basis set, (outer)core/valence correlation, scalar relativistic effects and a number of smaller effects. For thermochemical properties such as the heat of formation, the zero-point vibrational energy also becomes important, introducing its own set of difficulties to the computational approach. Changes in the various components as the chemical systems incorporate heavier elements and as the size of the systems grows are also considered. Finally, challenges arising from the desire to extend existing methods to transition metal and heavier elements are considered.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Dunning TH Jr (1989) J Chem Phys 90:1007

    Article  CAS  Google Scholar 

  2. Raghavachari K, Trucks GW, Pople JA, Head-Gordon M (1989) Chem Phys Lett 157:479

    Article  CAS  Google Scholar 

  3. Feller D, Peterson KA, Hill JG (2011) J Chem Phys 135:044102

    Article  CAS  Google Scholar 

  4. Pople JA, Head-Gordon M, Fox DJ, Raghavachari K, Curtiss LA (1989) J Chem Phys 90:5622

    Article  CAS  Google Scholar 

  5. Frisch MJ, Trucks GW, Head-Gordon M, Gill PMW, Wong MW, Foresman JB et al (1992) Gaussian 92. Gaussian, Inc., Pittsburg

  6. Curtiss LA, Jones C, Trucks GW, Raghavachari K, Pople JA (1990) J Chem Phys 93:2537

    Article  CAS  Google Scholar 

  7. Hehre WJ, Radom L, Schleyer PvR, Pople JA (1986) Ab initio molecular orbital theory. Wiley-Interscience, New York

    Google Scholar 

  8. Curtiss LA, Raghavachari K, Trucks GW, Pople JA (1991) J Chem Phys 94:7221

    Article  CAS  Google Scholar 

  9. Curtiss LA, Raghavachari K, Pople JA (1993) J Chem Phys 98:1293

    Article  CAS  Google Scholar 

  10. Bauschlicher CW Jr, Partridge H (1995) J Chem Phys 103:1788

    Article  CAS  Google Scholar 

  11. Smith BJ, Radon L (1995) J Phys Chem 99:6468

    Article  CAS  Google Scholar 

  12. Curtiss LA, Redfern PC, Smith BJ, Radom L (1996) J Chem Phys 104:5148

    Article  CAS  Google Scholar 

  13. Curtiss LA, Raghavachari K, Redfern PC, Pople JA (1998) J Chem Phys 109:7764

    Article  CAS  Google Scholar 

  14. Curtiss LA, Redfern PC, Raghavachari K, Rassolov V, Pople JA (1999) J Chem Phys 110:4703

    Article  CAS  Google Scholar 

  15. Baboul AG, Curtiss LA, Redfern PC, Raghavachari K (1999) J Chem Phys 110:7650

    Article  CAS  Google Scholar 

  16. Curtiss LA, Raghavachari K, Redfern PC, Baboul AG, Pople JA (1999) Chem Phys Lett 314:101

    Article  CAS  Google Scholar 

  17. Curtiss LA, Redfern PC, Raghavachari K, Pople JA (2001) J Chem Phys 114:108

    Article  CAS  Google Scholar 

  18. Henry DJ, Sullivan MB, Radom L (2003) J Chem Phys 118:4849

    Article  CAS  Google Scholar 

  19. Curtiss LA, Redfern PC, Raghavachari K (2007) J Chem Phys 126:084108

    Article  CAS  Google Scholar 

  20. Curtiss LA, Redfern PC, Raghavachari K (2007) J Chem Phys 127:124105

    Article  CAS  Google Scholar 

  21. Nyden MR, Petersson GA (1981) J Chem Phys 75:1843

    Article  CAS  Google Scholar 

  22. Petersson GA, Bennett A, Tensfeldt TG, Al-Laham MA, Shirley WA, Mantzaris J (1988) J Chem Phys 89:2193

    Article  CAS  Google Scholar 

  23. Petersson GA, Al-Laham MA (1991) J Chem Phys 94:6081

    Article  CAS  Google Scholar 

  24. Petersson GA, Tensfeldt TG, Montgomery JA Jr (1991) J Chem Phys 94:6091

    Article  CAS  Google Scholar 

  25. Montgomery JA Jr, Ochterski JW, Petersson GA (1994) J Chem Phys 101:5900

    Article  CAS  Google Scholar 

  26. Ochterski JW, Petersson GA, Montgomery JA Jr (1996) J Chem Phys 104:2598

    Article  CAS  Google Scholar 

  27. Montgomery JA Jr, Frisch MJ, Ochterski JW, Petersson GA (1999) J Chem Phys 110:2822

    Article  CAS  Google Scholar 

  28. Wood GPF, Radom L, Petersson GA, Barnes EC, Frisch MJ, Montgomery JA Jr (2006) J Chem Phys 125:094106

    Article  CAS  Google Scholar 

  29. Mayer PM, Parkinson CJ, Smith DM, Radom L (1998) J Chem Phys 108:604

    Article  CAS  Google Scholar 

  30. Martin JML, de Oliveira G (1999) J Chem Phys 111:1843

    Article  CAS  Google Scholar 

  31. Boese AD, Oren M, Atasoylu O, Martin JML, Kallay M, Gauss J (2004) J Chem Phys 120:4129

    Article  CAS  Google Scholar 

  32. Barnes EC, Petersson GA, Montgomery JJA, Frisch MJ, Martin JML (2009) J Chem Theory Comput 5:2687

    Article  CAS  Google Scholar 

  33. Karton A, Rabinovich E, Martin JML, Ruscic B (2006) J Chem Phys 125:144108

    Article  CAS  Google Scholar 

  34. Mintz B, Chan B, Sullivan MB, Buesgen T, Scott AP, Kass SR, Radom L, Wilson AK (2009) J Phys Chem A 113:9501

    Article  CAS  Google Scholar 

  35. Ruscic B (unpublished) Results obtained from the active thermochemical tables, ATcT ver. 1.25 and the Core (Argonne) thermochemical network ver. 1.056 2006

  36. Karton A, Taylor PR, Martin JML (2007) J Chem Phys 127:064104

    Article  CAS  Google Scholar 

  37. Karton A, Martin JML (2010) J Chem Phys 133:144102

    Article  CAS  Google Scholar 

  38. Tajti A, Szalay PG, Császár AG, Kállay M, Gauss J, Valeev EF, Flowers BA, Vázquez J, Stanton JF (2004) J Chem Phys 121:11599

    Article  CAS  Google Scholar 

  39. Helgaker T, Klopper W, Koch H, Noga J (1997) J Chem Phys 106:9639

    Article  CAS  Google Scholar 

  40. Bomble YJ, Vázquez J, Kállay M, Michauk C, Szalay PG, Császár AG, Gauss J, Stanton JF (2006) J Chem Phys 125:064108

    Article  CAS  Google Scholar 

  41. Harding ME, Vazquez J, Ruscic B, Wilson AK, Gauss J, Stanton JF (2008) J Chem Phys 128:114111

    Article  CAS  Google Scholar 

  42. DeYonker NJ, Cundari TR, Wilson AK (2006) J Chem Phys 124:114104

    Article  CAS  Google Scholar 

  43. Feller D (1992) J Chem Phys 96:6104

    Article  CAS  Google Scholar 

  44. Peterson KA, Woon DE, Dunning TH Jr (1994) J Chem Phys 100:7410

    Article  CAS  Google Scholar 

  45. Kedziora GS, Pople JA, Ratner MA, Redfern PC, Curtiss LA (2001) J Chem Phys 115:718

    Article  CAS  Google Scholar 

  46. DeYonker NJ, Grimes T, Yokel S, Dinescu A, Mintz B, Cundari TR, Wilson AK (2006) J Chem Phys 125:104111

    Article  CAS  Google Scholar 

  47. DeYonker NJ, Peterson KA, Steyl G, Wilson AK, Cundari TR (2007) J Phys Chem A 111:11269

    Article  CAS  Google Scholar 

  48. DeYonker NJ, Williams TG, Imel AE, Cundari TR, Wilson AK (2009) J Chem Phys 131:024106

    Article  CAS  Google Scholar 

  49. Mintz B, Williams TG, Howard L, Wilson AK (2009) J Chem Phys 130:234104

    Article  CAS  Google Scholar 

  50. Prascher BP, Lai JD, Wilson AK (2009) J Chem Phys 131:044130

    Article  CAS  Google Scholar 

  51. Schütz M, Chem J (2000) Phys 113:9986

    Google Scholar 

  52. Schütz M, Werner H-J (2000) Chem Phys Lett 318:370

    Article  Google Scholar 

  53. DeYonker NJ, Wilson BR, Pierpont AW, Cundari TR, Wilson AK (2009) Mol Phys 107:1107

    Article  CAS  Google Scholar 

  54. East ALL, Allen WD, Császár AG (1993) In: Laane J, van der Veken B, Overhammer H (eds) Structure and conformations of non-rigid molecules. Kluwer, Dordrecht, p 343

    Google Scholar 

  55. East ALL, Allen WD (1993) J Chem Phys 99:4638

    Article  CAS  Google Scholar 

  56. Császár AG, Allen WD, Schaefer HF, II I (1998) J Chem Phys 108:9751

    Article  Google Scholar 

  57. Cowan RD, Griffin M (1976) J Opt Soc Am 66:1010

    Article  CAS  Google Scholar 

  58. Handy NC, Yamaguchi Y, Schaefer HF (1986) J Chem Phys 84:4481

    Article  CAS  Google Scholar 

  59. Schuurman MS, Muir SR, Allen WD, Schaefer HF, II I (2004) J Chem Phys 120:11586

    Article  CAS  Google Scholar 

  60. East ALL, Johnson CS, Allen WD (1993) J Chem Phys 98:1299

    Article  CAS  Google Scholar 

  61. Feller D, Peterson KA, de Jong WA, Dixon DA (2003) J Chem Phys 118:3510

    Article  CAS  Google Scholar 

  62. Feller D, Peterson KA, Dixon DA (2008) J Chem Phys 129:204105

    Article  CAS  Google Scholar 

  63. Pollack L, Windus TL, de Jong WA, Dixon DA (2005) J Phys Chem A 109:6934

    Article  CAS  Google Scholar 

  64. Feller D, Peterson KA, Crawford TD (2006) J Chem Phys 124:054107

    Article  CAS  Google Scholar 

  65. Barnes EC, Petersson GA, Feller D, Peterson KA (2008) J Chem Phys 129:194115

    Article  CAS  Google Scholar 

  66. Feller D, Peterson KA, Dixon DA (2010) J Phys Chem A 114:61

    Article  CAS  Google Scholar 

  67. Feller D, Peterson KA, Dixon DA (2011) J Phys Chem A 115:1440

    Article  CAS  Google Scholar 

  68. Feller D, Peterson KA, Hill JG (2010) J Chem Phys 133:184102

    Article  CAS  Google Scholar 

  69. Feller D, Peterson KA (2007) J Chem Phys 126:114105

    Article  CAS  Google Scholar 

  70. Peterson KA, Dunning TH Jr (2002) J Chem Phys 117:10548

    Article  CAS  Google Scholar 

  71. Douglas M, Kroll NM (1974) Ann Phys NY 82:89

    Article  CAS  Google Scholar 

  72. Jansen G, Hess BA (1989) Phys Rev A 39:6016

    Article  Google Scholar 

  73. de Jong WA, Harrison RJ, Dixon DA (2001) J Chem Phys 114:48

    Article  Google Scholar 

  74. Dunham JL (1932) Phys Rev 41:713

    Article  CAS  Google Scholar 

  75. Kutzelnigg W (1997) Mol Phys 90:909

    Article  CAS  Google Scholar 

  76. Feller D, Craig NC, Matlin AR (2008) J Phys Chem A 112:2131

    Article  CAS  Google Scholar 

  77. Kendall RA, Dunning Jr TH, Harrison RJ (1992) J Chem Phys 96:6796

    Article  CAS  Google Scholar 

  78. Woon DE, Dunning TH Jr (1993) J Chem Phys 98:1358

    Article  CAS  Google Scholar 

  79. Peterson KA (2003) J Chem Phys 119:11099

    Article  CAS  Google Scholar 

  80. Feller D (1996) J Comp Chem 17:1571

    CAS  Google Scholar 

  81. Werner H-J, Knizia G, Adler TB, Marchetti O (2010) Z Phys Chem 224:493

    Article  CAS  Google Scholar 

  82. Klopper W, Manby FR, Ten-no S, Valeev EF (2006) Int Rev Phys Chem 25:427

    Article  CAS  Google Scholar 

  83. Knizia G, Adler TB, Werner H-J (2009) J Chem Phys 130:054104

    Article  CAS  Google Scholar 

  84. Peterson KA, Adler TB, Werner H-J (2008) J Chem Phys 128:084102

    Article  CAS  Google Scholar 

  85. Knizia G, Werner H-J (2008) J Chem Phys 128:154103

    Article  CAS  Google Scholar 

  86. Karton A, Martin JML (2006) Theor Chem Acc 115:330

    Article  CAS  Google Scholar 

  87. Schwenke DW (2005) J Chem Phys 122:014107

    Article  CAS  Google Scholar 

  88. Hill JG, Peterson KA, Knizia G, Werner H-J (2009) J Chem Phys 131:194105

    Article  CAS  Google Scholar 

  89. Woon DE, Dunning TH Jr (1995) J Chem Phys 103:4572

    Article  CAS  Google Scholar 

  90. Peterson KA, Yousaf KE (2010) J Chem Phys 133:174116

    Article  CAS  Google Scholar 

  91. Hill JG, Mazumder S, Peterson KA (2010) J Chem Phys 132:054108

    Article  CAS  Google Scholar 

  92. Peterson KA, Hill JG (2011) (in preparation)

  93. Balabanov NB, Peterson KA (2005) J Chem Phys 123:064107

    Article  CAS  Google Scholar 

  94. Bauschlicher Jr CW (1998) J Phys Chem A 102:10424

    Article  Google Scholar 

  95. Martin RL (1983) J Phys Chem 87:750

    Article  CAS  Google Scholar 

  96. Hess BA (1986) Phys Rev A 33:3742

    Article  CAS  Google Scholar 

  97. Kutzelnigg W, Ottschofski E, Franke R (1995) J Chem Phys 102:1740

    Article  CAS  Google Scholar 

  98. Tew DP, Klopper W, Heckert M, Gauss J (2007) J Phys Chem A 111:11242

    Article  CAS  Google Scholar 

  99. Boese AD, Oren M, Atasoylu O, Martin JML, Kallay M, Gauss J (2004) J Chem Phys 120:4129

    Article  CAS  Google Scholar 

  100. Bauschlicher CW Jr, Martin JML, Taylor PR (1999) J Phys Chem A 103:7715

    Article  CAS  Google Scholar 

  101. Michauk C, Gauss J (2007) J Chem Phys 127:044106

    Article  CAS  Google Scholar 

  102. Shepler BC, Balabanov NB, Peterson KA (2005) J Phys Chem A 109:10363

    Article  CAS  Google Scholar 

  103. Figgen D, Peterson KA, Dolg M, Stoll H (2009) J Chem Phys 130:164108

    Article  CAS  Google Scholar 

  104. Peterson KA, Figgen D, Dolg M, Stoll H (2007) J Chem Phys 126:124101

    Article  CAS  Google Scholar 

  105. Peterson KA, Puzzarini C (2005) Theor Chem Acc 114:283

    Article  CAS  Google Scholar 

  106. Peterson KA, Figgen D, Goll E, Stoll H, Dolg M (2003) J Chem Phys 119:11113

    Article  CAS  Google Scholar 

  107. Spohn B, Goll E, Stoll H, Figgen D, Peterson KA (2009) J Phys Chem A 113:12478

    Article  CAS  Google Scholar 

  108. Peterson KA, Shepler BC, Figgen D, Stoll H (2006) J Phys Chem A 110:13877

    Article  CAS  Google Scholar 

  109. Moore CE, (1971) Vol Natl Stand Ref Data Ser, National Bureau of Standards (US), Washington 35

  110. Hess BA, Marian CM, Peyerimhoff SD (1995) In: Yarkony DR (ed) Modern electronic structure theory, part I, vol 2. World Scientific, Singapore, p 152

    Chapter  Google Scholar 

  111. Shepler BC, Peterson KA (2003) J Phys Chem A 107:1783

    Article  CAS  Google Scholar 

  112. Yabushita S, Zhang Z, Pitzer RM (1999) J Phys Chem A 103:5791

    Article  CAS  Google Scholar 

  113. Cho WK, Choi YJ, Lee YS (2005) Mol Phys 103:925

    Article  CAS  Google Scholar 

  114. Ruden TA, Helgaker T, Jorgensen P, Olsen J (2003) Chem Phys Lett 371:62

    Article  CAS  Google Scholar 

  115. Ruscic B, Wagner AF, Harding LB, Asher RL, Feller D, Dixon DA, Peterson KA, Song Y, Qian XM, Ng CY, Liu JB, Chen WW (2002) J Phys Chem A 106:2727

    Article  CAS  Google Scholar 

  116. Gauss J, Tajti A, Kallay M, Stanton JF, Szalay PG (2006) J Chem Phys 125:4111

    Article  CAS  Google Scholar 

  117. Dyall KG, Bauschlicher Jr CW, Schwenke DW, Pyykkö P (2001) Chem Phys Lett 348:497

    Article  CAS  Google Scholar 

  118. Pyykkö P, Zhao U (2003) J Phys B 36:1469

    Article  Google Scholar 

  119. Barone V (2004) J Chem Phys 120:3059

    Article  CAS  Google Scholar 

  120. Karton A, Ruscic B, Martin JML (2007) J Mol Struct 811:345

    CAS  Google Scholar 

  121. Heckert M, Kallay M, Tew DP, Klopper W, Gauss J (2006) J Chem Phys 125:4108

    Article  CAS  Google Scholar 

  122. Puzzarini C (2009) J Phys Chem A 113:14530

    Article  CAS  Google Scholar 

  123. Peterson KA, Francisco JS (2011) J Chem Phys 134:084308

    Article  CAS  Google Scholar 

  124. Rauhut G, Knizia G, Werner H-J (2009) J Chem Phys 130:054105

    Article  CAS  Google Scholar 

  125. Puzzarini C, Barone V (2008) Phys Chem Chem Phys 2008:6991

    Article  CAS  Google Scholar 

  126. Barone V (2005) J Chem Phys 122:014108

    Article  CAS  Google Scholar 

  127. Clabo DA Jr, Schaefer HF III (1987) Int J Quantum Chem 31:429

    Article  CAS  Google Scholar 

  128. Rauhut G (2004) J Chem Phys 121:9313

    Article  CAS  Google Scholar 

  129. Puzzarini C, Heckert M, Gauss J (2008) J Chem Phys 128:194108

    Article  CAS  Google Scholar 

  130. Craig NC, Feller D, Groner P, Hsin HY, McKean DC, Nemchick DJ (2007) J Phys Chem A 111:2498

    Article  CAS  Google Scholar 

  131. Feller D, Craig NC (2009) J Phys Chem A 113:1601

    Article  CAS  Google Scholar 

  132. Feller D, Craig NC, Groner P, McKean DC (2011) J Phys Chem A 115:94

    Article  CAS  Google Scholar 

  133. Puzzarini C, Cazzoli G, Gambi A, Gauss J (2006) J Chem Phys 125:054307

    Article  CAS  Google Scholar 

  134. Craciun R, Picone D, Long RT, Li S, Dixon DA, Peterson KA, Christe KO (2010) Inorg Chem 49:1056

    Article  CAS  Google Scholar 

  135. Li S, Hennigan JM, Dixon DA, Peterson KA (2009) J Phys Chem A 113:7861

    Article  CAS  Google Scholar 

  136. Puzzarini C, Peterson KA (2005) Chem Phys 311:177

    Article  CAS  Google Scholar 

  137. Pahl E, Figgen D, Borschevsky A, Peterson KA, Schwerdtfeger P (2011) Theor Chem Acc 129:651

    Article  CAS  Google Scholar 

  138. Jiang W, Wilson AK (2011) J Chem Phys 134:034101

    Article  CAS  Google Scholar 

Download references

Acknowledgments

K. A. P. would like to acknowledge the funding of the National Science Foundation (CHE-0723997). D. A. D. was supported by the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, U.S. Department of Energy (DOE) under the catalysis center program. D. A. D. thanks the Robert Ramsay Fund of the University of Alabama and Argonne National Laboratory for partial support.

Author information

Authors and Affiliations

  1. Department of Chemistry, Washington State University, Pullman, WA, 99164-4630, USA

    Kirk A. Peterson & David Feller

  2. Department of Chemistry, The University of Alabama, Shelby Hall, Box 870336, Tuscaloosa, AL, 35487-0336, USA

    David A. Dixon

Authors
  1. Kirk A. Peterson
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. David Feller
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. David A. Dixon
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Kirk A. Peterson.

Additional information

Published as part of the special collection of articles celebrating the 50th anniversary of Theoretical Chemistry Accounts/Theoretica Chimica Acta.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Peterson, K.A., Feller, D. & Dixon, D.A. Chemical accuracy in ab initio thermochemistry and spectroscopy: current strategies and future challenges. Theor Chem Acc 131, 1079 (2012). https://doi.org/10.1007/s00214-011-1079-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00214-011-1079-5

Keywords

Search

Navigation