Understanding the Uniqueness of 2p Elements in Periodic Tables

Wang，Zhen Ling1; Hu，Han Shi1; von Szentpály，László2; Stoll，Hermann2; Fritzsche，Stephan3; Pyykkö，Pekka4; Schwarz，W. H.Eugen1,5; Li，Jun1,6

2020

10.1002/chem.202003920

CHEMISTRY-A EUROPEAN JOURNAL   影响因子和分区

0947-6539

1521-3765

The Periodic Table, and the unique chemical behavior of the first element in a column (group), were discovered simultaneously one and a half centuries ago. Half a century ago, this unique chemistry of the light homologs was correlated to the then available atomic orbital (AO) radii. The radially nodeless 1s, 2p, 3d, 4f valence AOs are particularly compact. The similarity of r(2s)≈r(2p) leads to pronounced sp-hybrid bonding of the light p-block elements, whereas the heavier p elements with n≥3 exhibit r(ns) ≪ r(np) of approximately −20 to −30 %. Herein, a comprehensive physical explanation is presented in terms of kinetic radial and angular, as well as potential nuclear-attraction and electron-screening effects. For hydrogen-like atoms and all inner shells of the heavy atoms, r(2s) ≫ r(2p) by +20 to +30 %, whereas r(3s)≳r(3p)≳r(3d), since in Coulomb potentials radial motion is more radial orbital expanding than angular motion. However, the screening of nuclear attraction by inner core shells is more efficient for s than for p valence shells. The uniqueness of the 2p AO is explained by this differential shielding. Thereby, the present work paves the way for future physical explanations of the 3d, 4f, and 5g cases.

bond theory orbital radii periodic table quantum chemistry radial node effect sp hybridization

SCI ; EI

英语

其他

National Natural Science Foundation of China[22033005] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Multidisciplinary

WOS:000589523300001

WILEY-V C H VERLAG GMBH

20204809551007

Atoms ; Electric fields ; Chemical bonds

Electricity: Basic Concepts and Phenomena:701.1 ; Physical Chemistry:801.4 ; Atomic and Molecular Physics:931.3

CHEMISTRY

2-s2.0-85096705423

Scopus

1.Department of Chemistry & Key Laboratory of Organic Optoelectronics,and Molecular Engineering of the Ministry of Education,Tsinghua University,Beijing,100084,China
2.Institut für Theoretische Chemie,Universität Stuttgart,Stuttgart,70550,Germany
3.Theoretisch-Physikalisches Institut,Universität Jena,Jena,07743,Germany
4.Department of Chemistry,University of Helsinki,POB 55,Helsinki,00014,Finland
5.Theoretische Chemie,Fachbereich Chemie-Biologie,Universität Siegen,Siegen,57068,Germany
6.Department of Chemistry,Southern University of Science and Technology,Shenzhen,518055,China

Wang，Zhen Ling,Hu，Han Shi,von Szentpály，László,et al. Understanding the Uniqueness of 2p Elements in Periodic Tables[J]. CHEMISTRY-A EUROPEAN JOURNAL,2020,26(67):15558-15564.

Wang，Zhen Ling.,Hu，Han Shi.,von Szentpály，László.,Stoll，Hermann.,Fritzsche，Stephan.,...&Li，Jun.(2020).Understanding the Uniqueness of 2p Elements in Periodic Tables.CHEMISTRY-A EUROPEAN JOURNAL,26(67),15558-15564.

Wang，Zhen Ling,et al."Understanding the Uniqueness of 2p Elements in Periodic Tables".CHEMISTRY-A EUROPEAN JOURNAL 26.67(2020):15558-15564.