Systematic convergence of energies with respect to basis set and treatment of electron correlation: focal-point conformational analysis of methanol

K. Kahn and T. C. Bruice

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Abstract

A practical means of overcoming the limitation in accuracy of conformational analysis due to incompleteness of basis sets used in ab initio calculations involves calculating the energy with a series of systematically improving basis sets and extrapolating to the basis set limit. We report here a focal-point conformational analysis for methanol. The Hartree–Fock energy converges exponentially to the basis set limit, while the convergence of second-order correlation energy is well described by the formula EcorX = Ecor¥ + A3 X - 3 + A5 X - 5 E^{\rm cor}_{X} = E^{\rm cor}_{\infty} + A_{3} X^{ - 3} + A_{5} X^{ - 5} . This formula also describes well the convergence of fourth-order correlation energy. The height of the rotational barrier at the Hartree–Fock level can be obtained reliably by taking the difference of the extrapolated energies of the two conformations and correcting the difference for correlation effects. Electron correlation has only a small decreasing effect on the height of the rotational barrier in methanol. The focal-point value for the torsional barrier in methanol is 0.999±0.007 kcal/mol.

Keywords:  Basis set extrapolation – Conformational analysis – Focal-point analysis – Torsional barrier – Methanol

Acknowledgement.enspThis project was supported by Provost Funds at University of California, Santa Barbara (UCSB). The computational resources were provided partially by the National Computational Science Alliance and UCSBrsquos Supercomputer Facility. We also acknowledge the Horgan Award (University of Missouri-Columbia) to K. K., which made possible the purchase of additional computational resources. We thank Robert Gdanitz and Bernie Kirtman for valuable discussions and Jozef Noga for providing us with a copy of the DIRCCR12-OS program.

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