problems / simon-ionization-excess

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Simon 2000 #9: bounded excess charge

In general

A nucleus of charge ZZ and NN electrons has Hamiltonian

H(N,Z)=∑i=1N(−12Δi−Z∣xi∣)+∑i<j1∣xi−xj∣H(N,Z)=\sum_{i=1}^{N}\Bigl(-\tfrac12\Delta_i-\frac{Z}{|x_i|}\Bigr)+\sum_{i<j}\frac1{|x_i-x_j|}

on the fermionic space. Write E(N,Z)E(N,Z) for the bottom of the spectrum. Binding means E(N,Z)<E(N−1,Z)E(N,Z)<E(N-1,Z). Let N0(Z)N_0(Z) (Simon) or Nc(Z)N_c(Z) (Nam, HPS) be the largest such NN. Zhislin proved binding whenever N<Z+1N<Z+1. Lieb proved Nc<2Z+1N_c<2Z+1. The ionization conjecture, Simon 2000 problem 9, asks for a ZZ-independent bound on the excess N0(Z)−ZN_0(Z)-Z.

Wikipedia is only a map. The published record is on arXiv.

Precise statement

Prove that N0(Z)−ZN_0(Z)-Z stays bounded as Z→∞Z\to\infty, or give a verified finite improvement of a published non-asymptotic upper bound on Nc(Z)N_c(Z).

The 1984 companion 10(a) asks for monotonicity of the ionization energy ΔE(N,Z)=E(N−1,Z)−E(N,Z)\Delta E(N,Z)=E(N-1,Z)-E(N,Z) in NN. A certified range where that inequality holds is useful; it is not a substitute for a bound on the excess.

Published record (fetched 2026-08-27)

After 2026-08-27

The same HPS Section 7 chain, with Lieb’s N/Z<2+1/Z≤9/4N/Z<2+1/Z\le9/4 on the Prop. 2.5 range Z≥4Z\ge4 and the exact b(3)b(3) in a1a_1, gives

N<b(3)Z+3.892 Z1/3+0.0134+0.184 Z−1/3+0.0196 Z−2/3(Z≥4)N<b(3)Z+3.892\,Z^{1/3}+0.0134+0.184\,Z^{-1/3}+0.0196\,Z^{-2/3}\qquad(Z\ge4)

and the simplified

Nc<1.1185Z+3.9781 Z1/3(Z≥4).N_c<1.1185Z+3.9781\,Z^{1/3}\qquad(Z\ge4).

Also Nc<b(2)Z+2.953Z1/3N_c<b(2)Z+2.953Z^{1/3} for Z≥2Z\ge2. This beats the printed remainders 3.90, 4, and 2.96. It does not beat the leading 1.1185. Replay: problems/simon-ionization-excess/compute/q1/run_all.sh.

N0(1)=2N_0(1)=2 is replayed (Hylleraas E=−815/1602<−1/2E=-815/1602<-1/2, plus Lieb). That uniqueness is already in Lieb 1984.

A later search (same day) replayed HPS v1, Nam, Lieb, and Benguria–González-Brantes arXiv:2511.07582v1 (N<1.4811Z+3.1516Z1/3N<1.4811Z+3.1516Z^{1/3} for Z≥12Z\ge12, bosonic / statistics- independent). That paper does not beat 1.11851.1185 for fermions. Two-shell dipoles make the HPS radialization form negative for every tested s>3s>3, so b(4)b(4) cannot be used. Lieb remains the best integer envelope at Z=2,3,4,5Z=2,3,4,5. A compact-aspect lower bound Q≥0.901924Q\ge0.901924 (aspect ≤4\le4) is certified and does not replace Theorem 2.2. A claimed 1.11681.1168 lift was withdrawn. Replay: problems/simon-ionization-excess/compute/q2/run_all.sh.

A third search the same day lifts the aspect-1212 compact bound Q≥0.899526Q\ge 0.899526 to every radial probability in HPS (4.1): mass-stationarity on a used support of aspect ≥12\ge 12 forces Q>12/13Q>12/13, and every atomic measure reduces to one of those two classes. Truncation plus spherical-shell approximation extends the bound. The same Section 7 chain with this β3\beta_3 gives

N<1.1118Z+3.880 Z1/3+0.0133+0.1833 Z−1/3+0.01956 Z−2/3(Z≥4)N<1.1118Z+3.880\,Z^{1/3}+0.0133+0.1833\,Z^{-1/3}+0.01956\,Z^{-2/3} \qquad(Z\ge 4)

and

Nc<1.1118Z+3.966 Z1/3(Z≥4).N_c<1.1118Z+3.966\,Z^{1/3}\qquad(Z\ge 4).

This beats the printed leading 1.11851.1185. It does not use the aspect-≤4\le 4 number 1.10871.1087 as an unrestricted bound, and it does not restore the withdrawn 1.11681.1168. Finite-ZZ integers and s>3s>3 stay residue. Replay: problems/simon-ionization-excess/compute/q3/run_all.sh.

A fourth search the same day keeps the mass-opt dichotomy and tightens the compact class: mid-radius faces at aspect 1010 with 2626 bins certify Q≥0.904414Q\ge 0.904414 (target φ=0.9091\varphi=0.9091). The cut Q>10/11Q>10/11 still exceeds that γ\gamma. The same Section 7 chain gives

N<1.1057Z+3.860 Z1/3+0.0132+0.1830 Z−1/3+0.01952 Z−2/3(Z≥4)N<1.1057Z+3.860\,Z^{1/3}+0.0132+0.1830\,Z^{-1/3}+0.01952\,Z^{-2/3} \qquad(Z\ge 4)

and

Nc<1.1057Z+3.946 Z1/3(Z≥4).N_c<1.1057Z+3.946\,Z^{1/3}\qquad(Z\ge 4).

This beats q3's 1.11181.1118 and the printed 1.11851.1185. The unrestricted leading sits below the aspect-≤4\le 4 class-only number 1.10871.1087; that class-only figure is not used as a bound. 1.11681.1168 stays withdrawn. Finite-ZZ integers and N0(Z)−ZN_0(Z)-Z stay residue. Replay: problems/simon-ionization-excess/compute/q4/run_all.sh.

A fifth search the same day keeps the mass-opt dichotomy at aspect 1010 and raises the mid-radius bin count to 3030. Faces certify Q≥0.906238Q\ge 0.906238 (target φ=0.9103\varphi=0.9103). The cut Q>10/11Q>10/11 still exceeds that γ\gamma. The same Section 7 chain gives

N<1.1035Z+3.855 Z1/3+0.01320+0.1828 Z−1/3+0.019510 Z−2/3(Z≥4)N<1.1035Z+3.855\,Z^{1/3}+0.01320+0.1828\,Z^{-1/3}+0.019510\,Z^{-2/3} \qquad(Z\ge 4)

and

Nc<1.1035Z+3.941 Z1/3(Z≥4).N_c<1.1035Z+3.941\,Z^{1/3}\qquad(Z\ge 4).

This beats q4's 1.10571.1057, q3's 1.11181.1118, and the printed 1.11851.1185. R≤9R\le 9 with the mass-opt cut cannot beat 1.10571.1057 and is residue. 1.11681.1168 stays withdrawn. Finite-ZZ integers and N0(Z)−ZN_0(Z)-Z stay residue. Replay: problems/simon-ionization-excess/compute/q5/run_all.sh.

A sixth search the same day keeps the mass-opt dichotomy at aspect 1010 and raises the mid-radius bin count to 3232. Faces certify Q≥0.906992Q\ge 0.906992 (target φ=0.9108\varphi=0.9108). The cut Q>10/11Q>10/11 still exceeds that γ\gamma. The same Section 7 chain gives

N<1.1026Z+3.853 Z1/3+0.01320+0.1828 Z−1/3+0.019500 Z−2/3(Z≥4)N<1.1026Z+3.853\,Z^{1/3}+0.01320+0.1828\,Z^{-1/3}+0.019500\,Z^{-2/3} \qquad(Z\ge 4)

and

Nc<1.1026Z+3.938 Z1/3(Z≥4).N_c<1.1026Z+3.938\,Z^{1/3}\qquad(Z\ge 4).

This beats q5's 1.10351.1035, q4's 1.10571.1057, q3's 1.11181.1118, and the printed 1.11851.1185. R≤9R\le 9 with the mass-opt cut cannot beat 1.10351.1035 and is residue. 1.11681.1168 stays withdrawn. Finite-ZZ integers and N0(Z)−ZN_0(Z)-Z stay residue. Replay: problems/simon-ionization-excess/compute/q6/run_all.sh.

A seventh search the same day keeps the mass-opt dichotomy at aspect 1010 and raises the mid-radius bin count to 3333. Faces certify Q≥0.907407Q\ge 0.907407 (target φ=0.9111\varphi=0.9111). The cut Q>10/11Q>10/11 still exceeds that γ\gamma. The same Section 7 chain gives

N<1.1021Z+3.851 Z1/3+0.01320+0.1828 Z−1/3+0.019500 Z−2/3(Z≥4)N<1.1021Z+3.851\,Z^{1/3}+0.01320+0.1828\,Z^{-1/3}+0.019500\,Z^{-2/3} \qquad(Z\ge 4)

and

Nc<1.1021Z+3.937 Z1/3(Z≥4).N_c<1.1021Z+3.937\,Z^{1/3}\qquad(Z\ge 4).

This beats q6's 1.10261.1026, q5's 1.10351.1035, q4's 1.10571.1057, q3's 1.11181.1118, and the printed 1.11851.1185. R≤9R\le 9 with the mass-opt cut cannot beat 1.10261.1026 and is residue. 1.11681.1168 stays withdrawn. Finite-ZZ integers and N0(Z)−ZN_0(Z)-Z stay residue. Replay: problems/simon-ionization-excess/compute/q7/run_all.sh.

An eighth search the same day keeps the mass-opt dichotomy at aspect 1010 and raises the face target on the n=33n=33 mid-radius matrix from 0.91110.9111 to 0.91120.9112. Faces certify Q≥0.907507Q\ge 0.907507 (target φ=0.9112\varphi=0.9112). The cut Q>10/11Q>10/11 still exceeds that γ\gamma. The same Section 7 chain gives

N<1.1020Z+3.851 Z1/3+0.01320+0.1828 Z−1/3+0.019500 Z−2/3(Z≥4)N<1.1020Z+3.851\,Z^{1/3}+0.01320+0.1828\,Z^{-1/3}+0.019500\,Z^{-2/3} \qquad(Z\ge 4)

and

Nc<1.1020Z+3.937 Z1/3(Z≥4).N_c<1.1020Z+3.937\,Z^{1/3}\qquad(Z\ge 4).

This beats q7's 1.10211.1021, q6's 1.10261.1026, q5's 1.10351.1035, q4's 1.10571.1057, q3's 1.11181.1118, and the printed 1.11851.1185. R≤9R\le 9 with the mass-opt cut cannot beat 1.10211.1021 and is residue. 1.11681.1168 stays withdrawn. Finite-ZZ integers and N0(Z)−ZN_0(Z)-Z stay residue. Replay: problems/simon-ionization-excess/compute/q8/run_all.sh.

A ninth search the same day keeps the mass-opt dichotomy at aspect 1010 and raises the mid-radius bin count to 3434. Faces certify Q≥0.907716Q\ge 0.907716 (target φ=0.9113\varphi=0.9113). The cut Q>10/11Q>10/11 still exceeds that γ\gamma. The same Section 7 chain gives

N<1.1017Z+3.850 Z1/3+0.01320+0.1827 Z−1/3+0.019500 Z−2/3(Z≥4)N<1.1017Z+3.850\,Z^{1/3}+0.01320+0.1827\,Z^{-1/3}+0.019500\,Z^{-2/3} \qquad(Z\ge 4)

and

Nc<1.1017Z+3.936 Z1/3(Z≥4).N_c<1.1017Z+3.936\,Z^{1/3}\qquad(Z\ge 4).

This beats q8's 1.10201.1020, q7's 1.10211.1021, q6's 1.10261.1026, q5's 1.10351.1035, q4's 1.10571.1057, q3's 1.11181.1118, and the printed 1.11851.1185. R≤9R\le 9 with the mass-opt cut cannot beat 1.10201.1020 and is residue. 1.11681.1168 stays withdrawn. Finite-ZZ integers and N0(Z)−ZN_0(Z)-Z stay residue. Replay: problems/simon-ionization-excess/compute/q9/run_all.sh.

A tenth search the same night keeps the mass-opt dichotomy at aspect 1010 and raises the mid-radius bin count to 3535. Faces certify Q≥0.908018Q\ge 0.908018 (target φ=0.9115\varphi=0.9115). The cut Q>10/11Q>10/11 still exceeds that γ\gamma. The same Section 7 chain gives

N<1.1013Z+3.849 Z1/3+0.01320+0.1827 Z−1/3+0.019500 Z−2/3(Z≥4)N<1.1013Z+3.849\,Z^{1/3}+0.01320+0.1827\,Z^{-1/3}+0.019500\,Z^{-2/3} \qquad(Z\ge 4)

and

Nc<1.1013Z+3.935 Z1/3(Z≥4).N_c<1.1013Z+3.935\,Z^{1/3}\qquad(Z\ge 4).

This beats q9's 1.10171.1017, q8's 1.10201.1020, q7's 1.10211.1021, q6's 1.10261.1026, q5's 1.10351.1035, q4's 1.10571.1057, q3's 1.11181.1118, and the printed 1.11851.1185. R≤9R\le 9 with the mass-opt cut cannot beat 1.10171.1017 and is residue. 1.11681.1168 stays withdrawn. Finite-ZZ integers and N0(Z)−ZN_0(Z)-Z stay residue. Replay: problems/simon-ionization-excess/compute/q10/run_all.sh.

An eleventh search the next morning keeps the mass-opt dichotomy at aspect 1010 and raises the mid-radius bin count to 3636. Faces certify Q≥0.908315Q\ge 0.908315 (target φ=0.9117\varphi=0.9117). The cut Q>10/11Q>10/11 still exceeds that γ\gamma. The same Section 7 chain gives

N<1.1010Z+3.849 Z1/3+0.01320+0.1827 Z−1/3+0.019490 Z−2/3(Z≥4)N<1.1010Z+3.849\,Z^{1/3}+0.01320+0.1827\,Z^{-1/3}+0.019490\,Z^{-2/3} \qquad(Z\ge 4)

and

Nc<1.1010Z+3.934 Z1/3(Z≥4).N_c<1.1010Z+3.934\,Z^{1/3}\qquad(Z\ge 4).

This beats q10's 1.10131.1013, q9's 1.10171.1017, q8's 1.10201.1020, q7's 1.10211.1021, q6's 1.10261.1026, q5's 1.10351.1035, q4's 1.10571.1057, q3's 1.11181.1118, and the printed 1.11851.1185. R≤9R\le 9 with the mass-opt cut cannot beat 1.10131.1013 and is residue. 1.11681.1168 stays withdrawn. Finite-ZZ integers and N0(Z)−ZN_0(Z)-Z stay residue. Replay: problems/simon-ionization-excess/compute/q11/run_all.sh.

A twelfth search the same day keeps the mass-opt dichotomy at aspect 1010 and starts n=37n=37 mid-radius bins, target φ=0.9119\varphi=0.9119. SLSQP predicts printed 1.10061.1006 if faces certify. The dump of 237−12^{37}-1 faces was stopped with the slowest shard at about 30%30\%. Scanned faces stay copositive and min⁡φ\min\varphi stays above 0.91190.9119; the rest of the mask space was not enumerated. Incomplete search is not a bound. Printed leading stays 1.10101.1010. R≤9R\le 9 with the mass-opt cut cannot beat 1.10101.1010 and is leftover. Finite-ZZ integers and N0(Z)−ZN_0(Z)-Z stay leftover. Replay: problems/simon-ionization-excess/compute/q12/run_all.sh.

A thirteenth search finishes n=37n=37 at the same split with a Gray-code enumerator in place of the incomplete mask dump. Faces 137,438,953,471137{,}438{,}953{,}471, copositive, 00 residual skips, min⁡φ=0.912085>0.9119\min\varphi=0.912085>0.9119. Compact γ=0.908606\gamma=0.908606, 1/γ=1.1005871/\gamma=1.100587, cut 10/11>γ10/11>\gamma. The same Section 7 chain gives

N<1.1006Z+3.848 Z1/3+0.01320+0.1827 Z−1/3+0.019490 Z−2/3(Z≥4)N<1.1006Z+3.848\,Z^{1/3}+0.01320+0.1827\,Z^{-1/3}+0.019490\,Z^{-2/3} \qquad(Z\ge 4)

and

Nc<1.1006Z+3.933 Z1/3(Z≥4).N_c<1.1006Z+3.933\,Z^{1/3}\qquad(Z\ge 4).

This beats q11's 1.10101.1010, q10's 1.10131.1013, q9's 1.10171.1017, q8's 1.10201.1020, q7's 1.10211.1021, q6's 1.10261.1026, q5's 1.10351.1035, q4's 1.10571.1057, q3's 1.11181.1118, and the printed 1.11851.1185. R≤9R\le 9 with the mass-opt cut cannot beat 1.10061.1006 and is leftover. 1.11681.1168 stays withdrawn. Finite-ZZ integers and N0(Z)−ZN_0(Z)-Z stay leftover. Replay: problems/simon-ionization-excess/compute/q13/run_all.sh.

2026-09-07 — rational matrix certificates

Two independent finite verifiers establish

Nc(Z)<1.1005Z+3.933Z1/3(Z≥4).N_c(Z)<1.1005Z+3.933Z^{1/3}\qquad(Z\ge4).

This is the inequality in q14/CLAIM.md. A raised target 0.9120.912 on 37 rational bins proves β3≥0.9087\beta_3\ge0.9087. Python verifies a positive-definite matrix and its entrywise nonnegative remainder with exact rational arithmetic. Rust checks a separate Gram witness using outward integer intervals. The same mass-stationary cut at aspect ten extends the compact result, and each implementation independently checks the HPS constants. The proof and replay require no earlier face-enumeration certificate. The leading 1.1005 improves q13's 1.1006 and HPS's printed 1.1185; bounded excess remains open.

Replay: problems/simon-ionization-excess/compute/q14/run_all.sh.

What would count as a new bound

The 2026-09-12 attempt with 40 bins stopped before numerical search and produced no new certificate. The bound above remains unchanged; see q15/CLAIM.md for the unproved target.

A verified inequality that strictly improves a published record, with a replayable certificate. Examples: a leading coefficient below 1.11851.1185 for all large ZZ; a remainder strictly below the printed 3.903.90 or 44 on the HPS range; Nc≤Z+CN_c\le Z+C for a universal CC; a unique exact N0(Z)N_0(Z) for some Z>1Z>1 that the published inequalities do not already settle.

What does not count

An incomplete variational or DFT search is not a lower bound. Restating HPS Proposition 2.5 is not a new bound. Hartree–Fock or DFT tables are heuristics. Simon 2000 #9 remains open unless the excess is shown bounded.