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Reliable radical stabilization energies from diffusion Monte Carlo calculations
Author(s) -
Per Manolo C.,
Fletcher Emily K.,
Swann Ellen T.,
Cleland Deidre M.
Publication year - 2020
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26397
Subject(s) - monte carlo method , benchmark (surveying) , wave function , quantum monte carlo , quantum chemical , diffusion monte carlo , diffusion , computational chemistry , set (abstract data type) , statistical physics , chemistry , hybrid monte carlo , mathematics , physics , thermodynamics , computer science , atomic physics , statistics , molecule , geodesy , organic chemistry , markov chain monte carlo , geography , programming language
We assess the performance of variational (VMC) and diffusion (DMC) quantum Monte Carlo methods for calculating the radical stabilization energies of a set of 43 carbon‐centered radical species. Even using simple single‐determinant trial wavefunctions, both methods perform exceptionally well, with mean absolute deviations from reference values well under the chemical accuracy standard of 1 kcal/mol. In addition, the use of DMC results in a highly concentrated spread of errors, with all 43 results within chemical accuracy at the 95% confidence level. These results indicate that DMC is an extremely reliable method for calculating radical stabilization energies and could be used as a benchmark method for larger systems in future.