Abstract
The development of better approximations to the exact exchange-correlation functional is essential to the accuracy of density functionals. A recent study suggested that functionals with few parameters provide more accurate electron densities than recently developed many-parameter functionals for light closed-shell atomic systems. In this study, we calculated electron densities, their gradients, and Laplacians of Ne, Ne6+, and Ne8+ using 19 electronic structure methods, and we compared them to the CCSD reference results. Two basis sets, namely, aug-cc-pωCV5Z and aug-cc-pV5Z, are utilized in the calculations. We found that the choice of basis set has a significant impact on the errors and rankings of some of the selected methods. The errors of electron densities, their gradients, and Laplacians calculated with the aug-cc-pV5Z basis set are substantially reduced, especially for Minnesota density functionals, as compared to the results using the aug-cc-pωCV5Z basis set (a larger basis set utilized in earlier work (Medvedev et al. Science 2017, 355, 49-52)). The rankings of the M06 suite of functionals among the 19 methods are greatly improved with the aug-cc-pV5Z basis set. In addition, the performances of the HSE06, BMK, MN12-L, and MN12-SX functionals are also improved with the aug-cc-pV5Z basis set. The M06 suite of functionals is capable of providing accurate electron densities, gradients, and Laplacians using the aug-cc-pV5Z basis set, and thus it is suitable for a wide range of applications in chemistry and physics.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 6068-6077 |
| Number of pages | 10 |
| Journal | Journal of Chemical Theory and Computation |
| Volume | 13 |
| Issue number | 12 |
| DOIs | |
| State | Published - Dec 12 2017 |
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How Well Can the M06 Suite of Functionals Describe the Electron Densities of Ne, Ne6+, and Ne8+? / Wang, Ying; Wang, Xianwei; Truhlar, Donald G; He, Xiao.
In: Journal of Chemical Theory and Computation, Vol. 13, No. 12, 12.12.2017, p. 6068-6077.Research output: Contribution to journal › Article
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TY - JOUR
T1 - How Well Can the M06 Suite of Functionals Describe the Electron Densities of Ne, Ne6+, and Ne8+?
AU - Wang, Ying
AU - Wang, Xianwei
AU - Truhlar, Donald G
AU - He, Xiao
PY - 2017/12/12
Y1 - 2017/12/12
N2 - The development of better approximations to the exact exchange-correlation functional is essential to the accuracy of density functionals. A recent study suggested that functionals with few parameters provide more accurate electron densities than recently developed many-parameter functionals for light closed-shell atomic systems. In this study, we calculated electron densities, their gradients, and Laplacians of Ne, Ne6+, and Ne8+ using 19 electronic structure methods, and we compared them to the CCSD reference results. Two basis sets, namely, aug-cc-pωCV5Z and aug-cc-pV5Z, are utilized in the calculations. We found that the choice of basis set has a significant impact on the errors and rankings of some of the selected methods. The errors of electron densities, their gradients, and Laplacians calculated with the aug-cc-pV5Z basis set are substantially reduced, especially for Minnesota density functionals, as compared to the results using the aug-cc-pωCV5Z basis set (a larger basis set utilized in earlier work (Medvedev et al. Science 2017, 355, 49-52)). The rankings of the M06 suite of functionals among the 19 methods are greatly improved with the aug-cc-pV5Z basis set. In addition, the performances of the HSE06, BMK, MN12-L, and MN12-SX functionals are also improved with the aug-cc-pV5Z basis set. The M06 suite of functionals is capable of providing accurate electron densities, gradients, and Laplacians using the aug-cc-pV5Z basis set, and thus it is suitable for a wide range of applications in chemistry and physics.
AB - The development of better approximations to the exact exchange-correlation functional is essential to the accuracy of density functionals. A recent study suggested that functionals with few parameters provide more accurate electron densities than recently developed many-parameter functionals for light closed-shell atomic systems. In this study, we calculated electron densities, their gradients, and Laplacians of Ne, Ne6+, and Ne8+ using 19 electronic structure methods, and we compared them to the CCSD reference results. Two basis sets, namely, aug-cc-pωCV5Z and aug-cc-pV5Z, are utilized in the calculations. We found that the choice of basis set has a significant impact on the errors and rankings of some of the selected methods. The errors of electron densities, their gradients, and Laplacians calculated with the aug-cc-pV5Z basis set are substantially reduced, especially for Minnesota density functionals, as compared to the results using the aug-cc-pωCV5Z basis set (a larger basis set utilized in earlier work (Medvedev et al. Science 2017, 355, 49-52)). The rankings of the M06 suite of functionals among the 19 methods are greatly improved with the aug-cc-pV5Z basis set. In addition, the performances of the HSE06, BMK, MN12-L, and MN12-SX functionals are also improved with the aug-cc-pV5Z basis set. The M06 suite of functionals is capable of providing accurate electron densities, gradients, and Laplacians using the aug-cc-pV5Z basis set, and thus it is suitable for a wide range of applications in chemistry and physics.
UR - http://www.scopus.com/inward/record.url?scp=85038256991&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85038256991&partnerID=8YFLogxK
U2 - 10.1021/acs.jctc.7b00865
DO - 10.1021/acs.jctc.7b00865
M3 - Article
C2 - 29111721
AN - SCOPUS:85038256991
VL - 13
SP - 6068
EP - 6077
JO - Journal of Chemical Theory and Computation
JF - Journal of Chemical Theory and Computation
SN - 1549-9618
IS - 12
ER -