Phosphorus mononitride: A difficult case for theory

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F19%3A00508902" target="_blank" >RIV/61388963:_____/19:00508902 - isvavai.cz</a>

Result on the web

<a href="https://onlinelibrary.wiley.com/doi/abs/10.1002/qua.26032" target="_blank" >https://onlinelibrary.wiley.com/doi/abs/10.1002/qua.26032</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/qua.26032" target="_blank" >10.1002/qua.26032</a>

Result language

angličtina

Original language name

Phosphorus mononitride: A difficult case for theory

Original language description

Phosphorus nitride (PN) is the simplest molecule formed solely by phosphorus and nitrogen. It represents an interesting model for materials, where phosphorus is directly attached to nitrogen. Nevertheless, both theoretical and experimental studies often provide an incomplete picture on the structural, electronic, and spectral properties of PN. Theoretical predictions often suffer from insufficient level of theory, incomplete basis set, or from neglecting several effects, for example, zero-point vibrational correction (ZPVC). Therefore, we performed an extensive benchmark study on structural, electronic, and spectral properties of PN at the Hartree-Fock, density functional theory (DFT), or even the coupled-cluster levels. We paid special attention to the basis set effect. We tested three variants of Dunning's aug-cc-pVXZ basis sets with the size from double-zeta to sextuple-zeta, as well as Jensen's aug-pc-n, aug-pcJ-n, and aug-pcSseg-n basis sets, where n = 1-4. Obtained energetics, PN distance, dipole moment, vibrational frequencies, and nuclear magnetic resonance (NMR) parameters were extrapolated to the complete basis set limit (CBS) using three- or two-parameter formulas. The P-31 NMR shieldings estimated with the aug-cc-pVXZ and aug-cc-pV(X + d)Z basis sets strongly depend on the basis set size providing scattered convergence patterns toward CBS. The Hartree-Fock self-consistent field (HF-SCF) NMR parameters evinced similar behavior as the coupled-cluster data. The only smooth convergence was achieved using the aug-cc-pCVXZ basis sets that include core-valence effects. The KT3 functional underestimated the phosphorus CBS shieldings by about 12 ppm compared to coupled cluster with singles and doubles (CCSD) (T). Nevertheless, KT3 unambiguously surpasses the HF-SCF and CCSD levels that provide P-31 shieldings that are lower by about 150 ppm and 24 ppm compared to CCSD(T). The convergence of nitrogen shieldings was regular for all basis set hierarchies and all theoretical methods. Relativistic and vibrational effects on selected properties were also discussed.

Czech name

—

Czech description

—

Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

<a href="/en/project/GA19-13436S" target="_blank" >GA19-13436S: Novel Insight into the Structure and Dynamics of Nucleic Acid Backbone by Means of Advanced DFT-MD Calculations and 31P NMR Spectroscopy</a><br>

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2019

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

International Journal of Quantum Chemistry

ISSN

0020-7608

e-ISSN

—

Volume of the periodical

119

Issue of the periodical within the volume

24

Country of publishing house

US - UNITED STATES

Number of pages

13

Pages from-to

e26032

UT code for WoS article

000482970700001

EID of the result in the Scopus database

2-s2.0-85071328566