2017/06/23 by Roland Assaraf, Assaraf, Roland, Saverio Moroni +3 · 2 citations
Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Advanced Physical and Chemical Molecular Interactions #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Quantum, superfluid, helium dynamics
paper · pdf · doi:10.48550/arxiv.1706.07588
openalex publication_date 2017/06/23 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
We present an improved formalism for quantum Monte Carlo calculations of\nenergy derivatives and properties (e.g. the interatomic forces), with a\nmultideterminant Jastrow-Slater function. As a function of the number Ne of\nSlater determinants, the numerical scaling of O(Ne) per derivative we have\nrecently reported is here lowered to O(Ne) for the entire set of\nderivatives. As a function of the number of electrons N, the scaling to\noptimize the wave function and the geometry of a molecular system is lowered to\nO(N3)+O(N Ne), the same as computing the energy alone in the sampling\nprocess. The scaling is demonstrated on linear polyenes up to C60H62\nand the efficiency of the method is illustrated with the structural\noptimization of butadiene and octatetraene with Jastrow-Slater wave functions\ncomprising as many as 200000 determinants and 60000 parameters.\n