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Molecule‐adapted basis sets optimized with a quantum Monte Carlo method
Author(s) -
Mendes Arruda Priscilla,
Canal Neto Antônio,
Martins Campos Mauro Cesar,
Coelho da Cruz Henrique Raulino,
Santos Fábio Alves
Publication year - 2015
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.24752
Subject(s) - basis set , basis (linear algebra) , simulated annealing , statistical physics , gaussian , basis function , monte carlo method , quantum monte carlo , molecular dynamics , wave function , set (abstract data type) , quantum , atom (system on chip) , computational chemistry , molecule , physics , chemistry , quantum mechanics , algorithm , mathematics , computer science , geometry , statistics , embedded system , programming language
The Monte Carlo simulated annealing method is adapted to optimize correlated Gaussian‐type functions in nonrelativistic molecular environments. Starting from an atom‐centered atomic Gaussian basis set, the uncontracted functions are reoptimized in the molecular environments corresponding to the H 2 O, CN − , N 2 , CO, BF, NO + , CO 2 , and CS systems. These new molecular adapted basis sets are used to calculate total energies, harmonic vibrational frequencies, and equilibrium geometries at a correlated level of theory. The present methodology is a simple and effective way to improve molecular correlated wave functions, without the need to enlarge the molecular basis set. Additionally, this methodology can be used to generate hierarchical sequences of molecular basis sets with increasing size, which are relevant to establish complete basis set limits. © 2014 Wiley Periodicals, Inc.