How do I pick a basis set for an ab-initio Hartree-Fock evaluation ? In other words, what are the important characteristics of a basis set so that a proper choice can be made ?
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asked Nov 29 '11 at 20:56
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$\begingroup$ I wonder why you are using Hartree-Fock at all. DFT is more accurate at the same computational cost so Hartree-Fock is primarily used only as the starting point for many-body calculations such as coupled-cluster. $\endgroup$ – Jeff Hammond Apr 13 '13 at 20:35
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This is a pretty big topic, but the basic important qualities of an atom-centered basis set are:
- The number of separate, unlinked functions it uses at the valence level (the so-called *zeta* count), which allow the modeling of that many different electronic environments, practically speaking.
- Additional higher angular momentum so-called *polarisation* functions to allow for more angular complexity.
- Whether it has diffuse functions to model more spacially extensive orbitals - so called *augmented* functions.
Generally, though, for Hartree-Fock:
- Double-zeta for very quick, very rough structural parameters.
- Double-zeta + polarisation for slightly less rough structural information, large systems (100+ atoms), or simple bonding environments like alkanes.
- Triple-zeta for better accuracy and useful energies.
- Augmented functions if you're working with anions.
Going to a better basis set than this for Hartree-Fock probably won't gain you much. In any case, unless you're moving on to a more complex method, you should probably be using density-functional theory (DFT) instead.
For more information on basis sets including how different basis sets are labelled, I recommend chapter 5.2 in Jensen's "Introduction to Computational Chemistry".
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$\begingroup$ Great answer. I would add A link from google books $\endgroup$ – Dr_bitz Nov 30 '11 at 8:51
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Here are some references that might be useful:
http://www.sciencedirect.com/science/article/pii/0167797785900036
http://books.google.com/books?id=Gt4pnp-UFhUC&lpg=PA853&vq=helgaker&pg=PA725#v=snippet&q=helgaker&f=false (if you see nothing, click next then prev). See http://www.worldscientific.com/doi/abs/10.1142/9789812832115_0001 to find the analog version in your library.
http://vergil.chemistry.gatech.edu/courses/chem6485/pdf/basis-sets.pdf
