TY - JOUR
T1 - Explicit large nuclear charge limit of electronic ground states forli, Be, B, C, N, O, F, Ne and basic aspects of the periodic table
AU - Friesecke, Gero
AU - Goddard, Benjamin D.
PY - 2009
Y1 - 2009
N2 - This paper is concerned with the Schrodinger equation for atoms and ions with N = 1 to 10 electrons. In the asymptotic limit of large nuclear charge Z, we determine explicitly the low-lying energy levels and eigenstates. The asymptotic energies and wavefunctions are in good quantitative agreement with experimental data for positive ions, and in excellent qualitative agreement even for neutral atoms (Z = N). In particular, the predicted ground state spin and angular momentum quantum numbers (1S for He, Be, Ne, 2S for H and Li, 4S for N, 2P for B and F, and 3P for C and O) agree with experiment in every case. The asymptotic Schrödinger ground states agree, up to small corrections, with the semiempirical hydrogen orbital configurations developed by Bohr, Hund, and Slater to explain the periodic table. In rare cases where our results deviate from this picture, such as the ordering of the lowest 1D° and 3S° states of the carbon isoelectronic sequence, experiment confirms our predictions and not Hund's.
AB - This paper is concerned with the Schrodinger equation for atoms and ions with N = 1 to 10 electrons. In the asymptotic limit of large nuclear charge Z, we determine explicitly the low-lying energy levels and eigenstates. The asymptotic energies and wavefunctions are in good quantitative agreement with experimental data for positive ions, and in excellent qualitative agreement even for neutral atoms (Z = N). In particular, the predicted ground state spin and angular momentum quantum numbers (1S for He, Be, Ne, 2S for H and Li, 4S for N, 2P for B and F, and 3P for C and O) agree with experiment in every case. The asymptotic Schrödinger ground states agree, up to small corrections, with the semiempirical hydrogen orbital configurations developed by Bohr, Hund, and Slater to explain the periodic table. In rare cases where our results deviate from this picture, such as the ordering of the lowest 1D° and 3S° states of the carbon isoelectronic sequence, experiment confirms our predictions and not Hund's.
KW - Aufbau principle
KW - Electronic structure
KW - Hund's rules
KW - Periodic table
KW - Quantum chemistry
KW - Schrödinger equation
UR - http://www.scopus.com/inward/record.url?scp=70450247361&partnerID=8YFLogxK
U2 - 10.1137/080729050
DO - 10.1137/080729050
M3 - Article
AN - SCOPUS:70450247361
SN - 0036-1410
VL - 41
SP - 631
EP - 664
JO - SIAM Journal on Mathematical Analysis
JF - SIAM Journal on Mathematical Analysis
IS - 2
ER -