The variationally stable procedure for Nth-order perturbative-transition-matrix elements introduced by the authors [Phys. Rev. Lett. 61, 404 (1988)] is presented here in detail. Its key features are that it is noniterative, involves only two unknown functions regardless of the value of N, is stable even near intermediate-state resonances (due to the presence of energy numerators rather than energy denominators), and uses the inverse of the perturbation operator for N\ensuremath{\ge}3. Explicit formulas are presented for application to high-order multiphoton processes in atomic hydrogen. Numerical results for multiphoton-ionization cross sections (for two, three, and seven photons), for the frequency dependence of the nonlinear susceptibilities for harmonic generation (for the third, fifth, and seventh harmonics), and for harmonic-generation transition rates up to 11th order for \ensuremath{\lambda}=1064 nm are presented for the atomic hydrogen ground state and compared with results of others by more standard procedures. We also present detailed analyses of the Z scaling of our results for hydrogenic systems, of the use of the imaginary part of the appropriate 2N-photon nonlinear susceptibility to obtain N-photon-ionization cross sections, and of the relation of the variational principle presented here to variational principles for scattering processes of Nuttall and Cohen [Phys. Rev. 188, 1542 (1969)] and of Schwinger [Phys. Rev. 72, 742 (1947)].The variationally stable procedure for Nth-order perturbative-transition-matrix elements introduced by the authors [Phys. Rev. Lett. 61, 404 (1988)] is presented here in detail. Its key features are that it is noniterative, involves only two unknown functions regardless of the value of N, is stable even near intermediate-state resonances (due to the presence of energy numerators rather than energy denominators), and uses the inverse of the perturbation operator for N\ensuremath{\ge}3. Explicit formulas are presented for application to high-order multiphoton processes in atomic hydrogen. Numerical results for multiphoton-ionization cross sections (for two, three, and seven photons), for the frequency dependence of the nonlinear susceptibilities for harmonic generation (for the third, fifth, and seventh harmonics), and for harmonic-generation transition rates up to 11th order for \ensuremath{\lambda}=1064 nm are presented for the atomic hydrogen ground state and compared with results of others by more standard procedures. We also present detailed analyses of the Z scaling of our results for hydrogenic systems, of the use of the imaginary part of the appropriate 2N-photon nonlinear susceptibility to obtain N-photon-ionization cross sections, and of the relation of the variational principle presented here to variational principles for scattering processes of Nuttall and Cohen [Phys. Rev. 188, 1542 (1969)] and of Schwinger [Phys. Rev. 72, 742 (1947)].

Physical Review AMay 1, 198965 citations

Dynamical susceptibilities in a strong coupling approach

Andrij M. Shvaika

arXiv:cond-mat/9912300Physica C SuperconductivityNov 1, 200024 citations

Certification failure in variational-principle observables

Ganga Singh Manchanda

Algorithms which prepare states via the variational principle assume that closeness in energy implies closeness in state; we formalise how this assumption can fail by showing that a ground-state energy estimate converged to within $ε$ of the true value is compatible with observable expectation values in error by up to $\sqrt{2εχ_O}$ at leading order, where $χ_O$ is the static susceptibility of the observable. As a result, the observable error can be orders of magnitude larger than the energy error, a mechanism we call non-linear error amplification, and because a variational algorithm cannot guarantee the correctness of these properties from energy alone, energy does not necessarily certify an observable. In light of our findings, we examine three algorithms: the variational quantum eigensolver on the transverse-field Ising chain, the density-matrix renormalisation group on a pair of weakly coupled hydrogen chains, and Krylov quantum diagonalisation on lithium fluoride. In each case we demonstrate that a well-converged energy can leave observables uncertified.Algorithms which prepare states via the variational principle assume that closeness in energy implies closeness in state; we formalise how this assumption can fail by showing that a ground-state energy estimate converged to within $ε$ of the true value is compatible with observable expectation values in error by up to $\sqrt{2εχ_O}$ at leading order, where $χ_O$ is the static susceptibility of the observable. As a result, the observable error can be orders of magnitude larger than the energy error, a mechanism we call non-linear error amplification, and because a variational algorithm cannot guarantee the correctness of these properties from energy alone, energy does not necessarily certify an observable. In light of our findings, we examine three algorithms: the variational quantum eigensolver on the transverse-field Ising chain, the density-matrix renormalisation group on a pair of weakly coupled hydrogen chains, and Krylov quantum diagonalisation on lithium fluoride. In each case we demonstrate that a well-converged energy can leave observables uncertified.

quant-pharXiv:2610.03989Oct 6, 20260 citations

A variational action principle

M. C. Smith-Agreda

PhysicaOct 1, 19640 citations

ε

of the true value is compatible with observable expectation values in error by up to

\sqrt{2εχ_O}

at leading order, where

χ_O

is the static susceptibility of the observable. As a result, the observable error can be orders of magnitude larger than the energy error, a mechanism we call non-linear error amplification, and because a variational algorithm cannot guarantee the correctness of these properties from energy alone, energy does not necessarily certify an observable. In light of our findings, we examine three algorithms: the variational quantum eigensolver on the transverse-field Ising chain, the density-matrix renormalisation group on a pair of weakly coupled hydrogen chains, and Krylov quantum diagonalisation on lithium fluoride. In each case we demonstrate that a well-converged energy can leave observables uncertified.