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The coupled-cluster description of electronic structure: perspectives for bioinorganic chemistry

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Abstract

This commentary provides an overview of the challenges and strengths of coupled-cluster theory when applied to active sites of metalloproteins. It is argued that thanks to increases in computer power and remarkable methodological developments, coupled-cluster methods will make increasingly important contributions to understanding the structure, properties and reactivity of transition metal cofactors.

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Notes

  1. As described here, the difference between CCSD and the configuration interaction with single and double excitations method, CISD, is not clear. The latter also includes single and double excitations. The difference resides in the exponential form of the excitation operator in coupled-cluster theory, so given two single excitation amplitudes, the wavefunction also includes the corresponding double excitation. Likewise, including double excitations intrinsically leads to accounting at least approximately for quadruple (and higher) excitations. The effect is to make CCSD a much more accurate and more useful method than CISD.

  2. On the basis of additional CCSD(T) calculations including extrapolation to the infinite basis set limit, and correlation of the 3s3p electrons [13], the CCSDT(Q)/cc-pVTZ value can be improved still further, leading to a ‘best’ zero-point-energy-corrected bond energy of 100.8 kcal/mol—it is noteworthy that this is significantly larger than the previously reported B3LYP value of 90.2 kcal/mol [12], showing again the value of accurate correlated methods for benchmarking.

  3. This statement may not remain true if multireference coupled-cluster methods, not discussed here, can make significant progress in terms of efficiency, accuracy and ease of use.

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  1. Centre for Computational Chemistry, School of Chemistry, University of Bristol, Cantock’s Close, Bristol, BS8 1TS, UK

    Jeremy N. Harvey

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  1. Jeremy N. Harvey
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Correspondence to Jeremy N. Harvey.

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Harvey, J.N. The coupled-cluster description of electronic structure: perspectives for bioinorganic chemistry. J Biol Inorg Chem 16, 831–839 (2011). https://doi.org/10.1007/s00775-011-0786-7

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