Computer Science Applications; Physical and Theoretical Chemistry
Abstract :
[en] We present full structural optimizations of the ground state and of the low lying triplet state of the ethylene molecule by means of Quantum Monte Carlo methods. Using the efficient structural optimization method based on renormalization techniques and on adjoint differentiation algorithms recently proposed [Sorella, S.; Capriotti, L. J. Chem. Phys.2010, 133, 234111], we present the variational convergence of both wave function parameters and atomic positions. All of the calculations were done using an accurate and compact wave function based on Pauling's resonating valence bond representation: the Jastrow Antisymmetrized Geminal Power (JAGP). All structural and wave function parameters are optimized, including coefficients and exponents of the Gaussian primitives of the AGP and the Jastrow atomic orbitals. Bond lengths and bond angles are calculated with a statistical error of about 0.1% and are in good agreement with the available experimental data. The Variational and Diffusion Monte Carlo calculations estimate vertical and adiabatic excitation energies in the ranges 4.623(10)-4.688(5) eV and 3.001(5)-3.091(5) eV, respectively. The adiabatic gap, which is in line with other correlated quantum chemistry methods, is slightly higher than the value estimated by recent photodissociation experiments. Our results demonstrate how Quantum Monte Carlo calculations have become a promising and computationally affordable tool for the structural optimization of correlated molecular systems.
Disciplines :
Chemistry
Author, co-author :
BARBORINI, Matteo ; University of Luxembourg > Faculty of Science, Technology and Medicine (FSTM) > HPC Platform ; Dipartimento di Chimica, Ingegneria Chimica e Materiali, Università degli studi dell'Aquila, Località Campo di Pile, 67100 L'Aquila, Italy
Sorella, Sandro; Scuola Internazionale Superiore di Studi Avanzati (SISSA) and Democritos National Simulation Center, Istituto Officina dei Materiali del CNR, via Bonomea 265, 34136 Trieste, Italy
Guidoni, Leonardo; Dipartimento di Chimica, Ingegneria Chimica e Materiali, Università degli studi dell'Aquila, Località Campo di Pile, 67100 L'Aquila, Italy
External co-authors :
yes
Language :
English
Title :
Structural Optimization by Quantum Monte Carlo: Investigating the Low-Lying Excited States of Ethylene.
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