A new electronic structure model is developed in which the ground state energy of a molecular system is given by a Hartree-Fock-like expression with parametrized one- and two-electron integrals over an extended (minimal + polarization) set of orthogonalized atom-centered basis functions, the variational equations being solved formally within the minimal basis but the effect of polarization functions being included in the spirit of second-order perturbation theory. It is designed to yield good dipole polarizabilities and improved intermolecular potentials with dispersion terms. The molecular integrals include up to three-center one-electron and two-center two-electron terms, all in simple analytical forms. A method to extract the effective one-electron Hamiltonian of nonlocal-exchange Kohn-Sham theory from the coupled-cluster one-electron density matrix is designed and used to get its matrix representation in a molecule-intrinsic minimal basis as an input to the parametrization procedure – making a direct link to the correlated wavefunction theory. The model has been trained for 15 elements (H, Li–F, Na–Cl, 720 parameters) on a set of 5581 molecules (including ions, transition states, and weakly bound complexes) whose first- and second-order properties were computed by the coupled-cluster theory as a reference, and a good agreement is seen. The model looks promising for the study of large molecular systems, it is believed to be an important step forward from the traditional semiempirical models towards higher accuracy at nearly as low a computational cost.
Skip Nav Destination
Article navigation
7 October 2011
Research Article|
October 07 2011
A new parametrizable model of molecular electronic structure
Dimitri N. Laikov
Dimitri N. Laikov
a)
Chemistry Department,
Moscow State University
, 119992 Moscow, Russia
Search for other works by this author on:
a)
Electronic mail: [email protected]. URL: http://rad.chem.msu.ru/~laikov/.
J. Chem. Phys. 135, 134120 (2011)
Article history
Received:
June 23 2011
Accepted:
September 14 2011
Connected Content
A related article has been published:
Comment on “A new parametrizable model of molecular electronic structure” [J. Chem. Phys. 135, 134120 (2011)]
Citation
Dimitri N. Laikov; A new parametrizable model of molecular electronic structure. J. Chem. Phys. 7 October 2011; 135 (13): 134120. https://doi.org/10.1063/1.3646498
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Related Content
Weakly parametrized Jastrow ansatz for a strongly correlated Bose system
J. Chem. Phys. (March 2017)
Water interactions with hydrophobic groups: Assessment and recalibration of semiempirical molecular orbital methods
J. Chem. Phys. (July 2014)
Density-functional expansion methods: Evaluation of LDA, GGA, and meta-GGA functionals and different integral approximations
J. Chem. Phys. (December 2010)
Improving intermolecular interactions in DFTB3 using extended polarization from chemical-potential equalization
J. Chem. Phys. (August 2015)