Assessment of density functional theory in predicting structures and free energies of reaction of atmospheric prenucleation clusters

Jonas Elm; Merete Bilde; Kurt Valentin Mikkelsen

doi:10.1021/ct300192p

Assessment of density functional theory in predicting structures and free energies of reaction of atmospheric prenucleation clusters

Jonas Elm, Merete Bilde, Kurt Valentin Mikkelsen

Kemisk Institut

120 Citationer (Scopus)

Abstract

This work assesses different computational strategies for predicting structures and Gibbs free energies of reaction of atmospheric prenucleation clusters. The performance of 22 Density Functional Theory functionals in predicting equilibrium structures of molecules and water prenucleation clusters of atmospheric relevance is evaluated against experimental data using a test set of eight molecules and prenucleation clusters: SO ₂, H ₂SO ₄, CO ₂·H ₂O, CS ₂·H ₂O, OCS·H ₂O, SO ₂·H ₂O, SO ₃·H ₂O, and H ₂SO ₄·H ₂O. Furthermore, the functionals are tested and compared for their ability to predict the free energy of reaction for the formation of five benchmark atmospheric prenucleation clusters: H ₂SO ₄·H ₂O, H ₂SO ₄·(H ₂O) ₂, H ₂SO ₄·NH ₃, HSO ₄ ^-·H ₂O, and HSO ₄ ^-·(H ₂O) ₂. The performance is evaluated against experimental data, coupled cluster, and complete basis set extrapolation procedure methods. Our investigation shows that the utilization of the M06-2X functional with the 6-311++G(3df,3pd) basis set represents an improved approach compared to the conventionally used PW91 functional, yielding mean absolute errors of 0.48 kcal/mol and maximum errors of 0.67 kcal/mol compared to experimental results.

Originalsprog	Engelsk
Tidsskrift	Journal of Chemical Theory and Computation
Vol/bind	8
Udgave nummer	6
Sider (fra-til)	2071-2077
Antal sider	7
ISSN	1549-9618
DOI	https://doi.org/10.1021/ct300192p
Status	Udgivet - 12 jun. 2012

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10.1021/ct300192p

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title = "Assessment of density functional theory in predicting structures and free energies of reaction of atmospheric prenucleation clusters",

abstract = "This work assesses different computational strategies for predicting structures and Gibbs free energies of reaction of atmospheric prenucleation clusters. The performance of 22 Density Functional Theory functionals in predicting equilibrium structures of molecules and water prenucleation clusters of atmospheric relevance is evaluated against experimental data using a test set of eight molecules and prenucleation clusters: SO 2, H 2SO 4, CO 2·H 2O, CS 2·H 2O, OCS·H 2O, SO 2·H 2O, SO 3·H 2O, and H 2SO 4·H 2O. Furthermore, the functionals are tested and compared for their ability to predict the free energy of reaction for the formation of five benchmark atmospheric prenucleation clusters: H 2SO 4·H 2O, H 2SO 4·(H 2O) 2, H 2SO 4·NH 3, HSO 4 -·H 2O, and HSO 4 -·(H 2O) 2. The performance is evaluated against experimental data, coupled cluster, and complete basis set extrapolation procedure methods. Our investigation shows that the utilization of the M06-2X functional with the 6-311++G(3df,3pd) basis set represents an improved approach compared to the conventionally used PW91 functional, yielding mean absolute errors of 0.48 kcal/mol and maximum errors of 0.67 kcal/mol compared to experimental results.",

author = "Jonas Elm and Merete Bilde and Mikkelsen, {Kurt Valentin}",

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AU - Elm, Jonas

AU - Bilde, Merete

AU - Mikkelsen, Kurt Valentin

PY - 2012/6/12

Y1 - 2012/6/12

N2 - This work assesses different computational strategies for predicting structures and Gibbs free energies of reaction of atmospheric prenucleation clusters. The performance of 22 Density Functional Theory functionals in predicting equilibrium structures of molecules and water prenucleation clusters of atmospheric relevance is evaluated against experimental data using a test set of eight molecules and prenucleation clusters: SO 2, H 2SO 4, CO 2·H 2O, CS 2·H 2O, OCS·H 2O, SO 2·H 2O, SO 3·H 2O, and H 2SO 4·H 2O. Furthermore, the functionals are tested and compared for their ability to predict the free energy of reaction for the formation of five benchmark atmospheric prenucleation clusters: H 2SO 4·H 2O, H 2SO 4·(H 2O) 2, H 2SO 4·NH 3, HSO 4 -·H 2O, and HSO 4 -·(H 2O) 2. The performance is evaluated against experimental data, coupled cluster, and complete basis set extrapolation procedure methods. Our investigation shows that the utilization of the M06-2X functional with the 6-311++G(3df,3pd) basis set represents an improved approach compared to the conventionally used PW91 functional, yielding mean absolute errors of 0.48 kcal/mol and maximum errors of 0.67 kcal/mol compared to experimental results.

AB - This work assesses different computational strategies for predicting structures and Gibbs free energies of reaction of atmospheric prenucleation clusters. The performance of 22 Density Functional Theory functionals in predicting equilibrium structures of molecules and water prenucleation clusters of atmospheric relevance is evaluated against experimental data using a test set of eight molecules and prenucleation clusters: SO 2, H 2SO 4, CO 2·H 2O, CS 2·H 2O, OCS·H 2O, SO 2·H 2O, SO 3·H 2O, and H 2SO 4·H 2O. Furthermore, the functionals are tested and compared for their ability to predict the free energy of reaction for the formation of five benchmark atmospheric prenucleation clusters: H 2SO 4·H 2O, H 2SO 4·(H 2O) 2, H 2SO 4·NH 3, HSO 4 -·H 2O, and HSO 4 -·(H 2O) 2. The performance is evaluated against experimental data, coupled cluster, and complete basis set extrapolation procedure methods. Our investigation shows that the utilization of the M06-2X functional with the 6-311++G(3df,3pd) basis set represents an improved approach compared to the conventionally used PW91 functional, yielding mean absolute errors of 0.48 kcal/mol and maximum errors of 0.67 kcal/mol compared to experimental results.

U2 - 10.1021/ct300192p

DO - 10.1021/ct300192p

M3 - Journal article

SN - 1549-9618

VL - 8

SP - 2071

EP - 2077

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

IS - 6

ER -

Assessment of density functional theory in predicting structures and free energies of reaction of atmospheric prenucleation clusters

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