Development of polarization consistent basis sets for spin-spin coupling constant calculations for the atoms Li, Be, Na, and Mg

Patrick Alexander Aggelund; Stephan P. A. Sauer; Frank Jensen

doi:10.1063/1.5034109

Development of polarization consistent basis sets for spin-spin coupling constant calculations for the atoms Li, Be, Na, and Mg

Patrick Alexander Aggelund, Stephan P. A. Sauer, Frank Jensen

Department of Chemistry

8 Citations (Scopus)

105 Downloads (Pure)

Abstract

The pcJ-n basis set, optimized for spin-spin coupling constant calculations using density functional theory methods, are expanded to also include the s-block elements Li, Be, Na, and Mg, by studying several small molecules containing these elements. This is done by decontracting the underlying pc-n basis sets, followed by augmentation with additional tight functions. As was the case for the p-block elements, the convergence of the results can be significantly improved by augmentation with tight s-functions. For the p-block elements additional tight functions of higher angular momentum were also needed, but this is not the case for the s-block elements. A search for the optimum contraction scheme is carried out using the criterion that the contraction error should be lower than the inherent error of the uncontracted pcJ-n relative to the uncontracted pcJ-4 basis set. A large search over possible contraction schemes is done for the Li2 and Na2 molecules, and based on this search contracted pcJ-n basis sets for the four atoms are recommended. This work shows that it is more difficult to contract the pcJ-n basis sets, than the underlying pc-n basis sets. However, it also shows that the pcJ-n basis sets for Li and Be can be more strongly contracted than the pcJ-n basis sets for the p-block elements. For Na and Mg, the contractions are to the same degree as for the p-block elements.

Original language	English
Article number	044117
Journal	The Journal of Chemical Physics
Volume	149
Issue number	4
Pages (from-to)	1-10
Number of pages	10
ISSN	0021-9606
DOIs	https://doi.org/10.1063/1.5034109
Publication status	Published - 28 Jul 2018

Keywords

Faculty of Science
basis set
NMR
Spin-spin coupling constant
DFT calculations

Access to Document

10.1063/1.5034109

Manuscript-acceptedAccepted author manuscript, 173 KB

Cite this

@article{f96e050f788c43538b36d5e0e39dcea9,

title = "Development of polarization consistent basis sets for spin-spin coupling constant calculations for the atoms Li, Be, Na, and Mg",

abstract = "The pcJ-n basis set, optimized for spin-spin coupling constant calculations using density functional theory methods, are expanded to also include the s-block elements Li, Be, Na, and Mg, by studying several small molecules containing these elements. This is done by decontracting the underlying pc-n basis sets, followed by augmentation with additional tight functions. As was the case for the p-block elements, the convergence of the results can be significantly improved by augmentation with tight s-functions. For the p-block elements additional tight functions of higher angular momentum were also needed, but this is not the case for the s-block elements. A search for the optimum contraction scheme is carried out using the criterion that the contraction error should be lower than the inherent error of the uncontracted pcJ-n relative to the uncontracted pcJ-4 basis set. A large search over possible contraction schemes is done for the Li2 and Na2 molecules, and based on this search contracted pcJ-n basis sets for the four atoms are recommended. This work shows that it is more difficult to contract the pcJ-n basis sets, than the underlying pc-n basis sets. However, it also shows that the pcJ-n basis sets for Li and Be can be more strongly contracted than the pcJ-n basis sets for the p-block elements. For Na and Mg, the contractions are to the same degree as for the p-block elements.",

keywords = "Faculty of Science, basis set, NMR, Spin-spin coupling constant, DFT calculations",

author = "Aggelund, {Patrick Alexander} and Sauer, {Stephan P. A.} and Frank Jensen",

year = "2018",

month = jul,

day = "28",

doi = "10.1063/1.5034109",

language = "English",

volume = "149",

pages = "1--10",

journal = "The Journal of Chemical Physics",

issn = "0021-9606",

publisher = "American Institute of Physics",

number = "4",

}

TY - JOUR

T1 - Development of polarization consistent basis sets for spin-spin coupling constant calculations for the atoms Li, Be, Na, and Mg

AU - Aggelund, Patrick Alexander

AU - Sauer, Stephan P. A.

AU - Jensen, Frank

PY - 2018/7/28

Y1 - 2018/7/28

N2 - The pcJ-n basis set, optimized for spin-spin coupling constant calculations using density functional theory methods, are expanded to also include the s-block elements Li, Be, Na, and Mg, by studying several small molecules containing these elements. This is done by decontracting the underlying pc-n basis sets, followed by augmentation with additional tight functions. As was the case for the p-block elements, the convergence of the results can be significantly improved by augmentation with tight s-functions. For the p-block elements additional tight functions of higher angular momentum were also needed, but this is not the case for the s-block elements. A search for the optimum contraction scheme is carried out using the criterion that the contraction error should be lower than the inherent error of the uncontracted pcJ-n relative to the uncontracted pcJ-4 basis set. A large search over possible contraction schemes is done for the Li2 and Na2 molecules, and based on this search contracted pcJ-n basis sets for the four atoms are recommended. This work shows that it is more difficult to contract the pcJ-n basis sets, than the underlying pc-n basis sets. However, it also shows that the pcJ-n basis sets for Li and Be can be more strongly contracted than the pcJ-n basis sets for the p-block elements. For Na and Mg, the contractions are to the same degree as for the p-block elements.

AB - The pcJ-n basis set, optimized for spin-spin coupling constant calculations using density functional theory methods, are expanded to also include the s-block elements Li, Be, Na, and Mg, by studying several small molecules containing these elements. This is done by decontracting the underlying pc-n basis sets, followed by augmentation with additional tight functions. As was the case for the p-block elements, the convergence of the results can be significantly improved by augmentation with tight s-functions. For the p-block elements additional tight functions of higher angular momentum were also needed, but this is not the case for the s-block elements. A search for the optimum contraction scheme is carried out using the criterion that the contraction error should be lower than the inherent error of the uncontracted pcJ-n relative to the uncontracted pcJ-4 basis set. A large search over possible contraction schemes is done for the Li2 and Na2 molecules, and based on this search contracted pcJ-n basis sets for the four atoms are recommended. This work shows that it is more difficult to contract the pcJ-n basis sets, than the underlying pc-n basis sets. However, it also shows that the pcJ-n basis sets for Li and Be can be more strongly contracted than the pcJ-n basis sets for the p-block elements. For Na and Mg, the contractions are to the same degree as for the p-block elements.

KW - Faculty of Science

KW - basis set

KW - NMR

KW - Spin-spin coupling constant

KW - DFT calculations

UR - http://www.scopus.com/inward/record.url?scp=85051089813&partnerID=8YFLogxK

U2 - 10.1063/1.5034109

DO - 10.1063/1.5034109

M3 - Journal article

C2 - 30068157

SN - 0021-9606

VL - 149

SP - 1

EP - 10

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

IS - 4

M1 - 044117

ER -

Development of polarization consistent basis sets for spin-spin coupling constant calculations for the atoms Li, Be, Na, and Mg

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this