article · Journal of Chemical Theory and Computation · 2008

Anchoring the Absolute Proton Affinity Scale

Gábor Czakó, Edit Mátyus, Andrew C. Simmonett, Attila G. Császár, Henry F. Schaefer, Wesley D. Allen

Cited by 45Abstract and details only

Abstract

Converged first-principles proton affinities (PA) of ammonia and carbon monoxide have been determined by the focal-point analysis (FPA) approach, thus fixing the high and low ends of the molecular proton affinity scale. The electronic structure computations employed the all-electron (AE) coupled-cluster (CC) method up to single, double, triple, quadruple, and pentuple excitations. Aug-cc-pCVXZ [X = 2(D), 3(T), 4(Q), 5, and 6] correlation-consistent (cc) Gaussian basis sets for C, N, and O were used in conjunction with the corresponding aug-cc-pVXZ (X = 2-6) sets for H. Our FPA study supersedes previous computational work by accounting for (a) electron correlation beyond the "gold standard" CCSD(T) level; (b) the nonadditivity of core electron correlation effects; (c) scalar relativity; (d) diagonal Born-Oppenheimer corrections (DBOC); (e) anharmonicity of zero-point vibrational energies, based on accurate AE-CCSD(T)/cc-pCVQZ internal coordinate quartic force fields and fully variational vibrational computations; and (f) thermal corrections to enthalpies by direct summation over rovibrational energy levels. Our final proton affinities at 298.15(0.0) K are ΔpaH°(NH3) = 852.6(846.4) ± 0.3 kJ mol(-1) and ΔpaH°(CO) = 592.4(586.5) ± 0.2 kJ mol(-1). These values have better accuracy and considerably lower uncertainty than the best previous recommendations and thus anchor the proton affinity scale of molecules for future use.

Cite this paper

APA 7

Czakó, G., Mátyus, E., Simmonett, A. C., Császár, A. G., Schaefer, H. F., & Allen, W. D. (2008). Anchoring the Absolute Proton Affinity Scale. Journal of Chemical Theory and Computation, 4(8), 1220–1229. https://doi.org/10.1021/ct800082r

MLA 9

Czakó, Gábor, et al. “Anchoring the Absolute Proton Affinity Scale.” Journal of Chemical Theory and Computation, vol. 4, no. 8, 2008, pp. 1220–29, https://doi.org/10.1021/ct800082r.

Chicago

Czakó, Gábor, Edit Mátyus, Andrew C. Simmonett, Attila G. Császár, Henry F. Schaefer, and Wesley D. Allen. 2008. “Anchoring the Absolute Proton Affinity Scale.” Journal of Chemical Theory and Computation 4 (8): 1220–29. https://doi.org/10.1021/ct800082r.

Harvard

Czakó, G. et al. (2008) ‘Anchoring the Absolute Proton Affinity Scale’, Journal of Chemical Theory and Computation, 4(8), pp. 1220–1229. Available at: https://doi.org/10.1021/ct800082r.

BibTeX

@article{czako2008anchoring,
  title = {{Anchoring the Absolute Proton Affinity Scale}},
  author = {Czakó, Gábor and Mátyus, Edit and Simmonett, Andrew C. and Császár, Attila G. and Schaefer, Henry F. and Allen, Wesley D.},
  journal = {Journal of Chemical Theory and Computation},
  volume = {4},
  number = {8},
  pages = {1220--1229},
  year = {2008},
  doi = {10.1021/ct800082r}
}

Made from the index record. Check names, capitalisation and page numbers against the paper. Need another style? AI for Research has over 10,000.