Alternative wavefunction ansatz for including explicit electron-proton correlation in the nuclear-electronic orbital approach

作者：Ko Chaehyuk; Pak Michael V; Swalina Chet; Hammes Schiffer Sharon^*

来源：Journal of Chemical Physics, 2011, 135(5): 054106.

DOI：10.1063/1.3611054

• approximation theory
• electron correlations
• Gaussian processes
• HF calculations
• optimisation
• orbital calculations
• potential energy surfaces
• variational techniques
• wave functions

The nuclear-electronic orbital (NEO) approach treats specified nuclei quantum mechanically on the same level as the electrons with molecular orbital techniques. The explicitly correlated Hartree-Fock (NEO-XCHF) approach was developed to incorporate electron-nucleus dynamical correlation directly into the variational optimization of the nuclear-electronic wavefunction. In the original version of this approach, the Hartree-Fock wavefunction is multiplied by (1+(G) over cap), where (G) over cap is a geminal operator expressed as a sum of Gaussian type geminal functions that depend on the electron-proton distance. Herein, a new wavefunction ansatz is proposed to avoid the computation of five- and six-particle integrals and to simplify the computation of the lower dimensional integrals involving the geminal functions. In the new ansatz, denoted NEO-XCHF2, the Hartree-Fock wavefunction is multiplied by root 1 + (G) over cap rather than (1+(G) over cap). Although the NEO-XCHF2 ansatz eliminates the integrals that are quadratic in the geminal functions, it introduces terms in the kinetic energy integrals with no known analytical solution. A truncated expansion scheme is devised to approximate these problematic terms. An alternative hybrid approach, in which the kinetic energy terms are calculated with the original NEO-XCHF ansatz and the potential energy terms are calculated with the NEO-XCHF2 ansatz, is also implemented. Applications to a series of model systems with up to four electrons provide validation for the NEO-XCHF2 approach and the treatments of the kinetic energy terms.

• 出版日期2011-8-7