Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Log inSign up
Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Blog
Job Board
Q3AS

© 2026 Aqora Quantum S.A.S.

TermsPrivacyLegal Notice

arXiv:2602.21299

Ab Initio Random Matrix Theory of Molecular Electronic Structure

Zhen Tao, Victor Galitski

cond-mat.str-elphysics.chem-phphysics.comp-phquant-phSubmitted Feb 24, 2026• Announced Feb 26, 2026• 0 citations
arXivHTMLPDF

Abstract

We use ab initio electronic-structure methods to investigate random-matrix theory (RMT) universality in molecular electronic structure. Using single-reference electronic structure methods, including Hartree-Fock, configuration-interaction singles (CIS), density functional theory, and linear-response time-dependent density-functional theory, we compute single-particle orbital energies and many-electron excitations of several representative molecules (benzene, alanine, 1-phenylethylamine, methyloxirane, and helicene chains). For generic low-symmetry geometries, the unfolded spectra of these ab initio Hamiltonians exhibit Wigner-Dyson level statistics of the Gaussian orthogonal ensemble (GOE). For extended helicene chains we explicitly restrict to bound valence excitations below the ionization threshold and still observe GOE statistics, indicating that the RMT universality is present for physical states of direct relevance to real molecules. We further explore the electric and magnetic field dependence of the molecular electronic spectra. The variance of electric polarizability (level curvature K) is predicted to be non-analytic in the magnetic field which serves as an infrared cutoff, <K^2> proportional to log(1/|B|). We observe a transition to the Gaussian unitary ensemble (GUE) by increasing the magnetic fields, although it occurs only at magnetic fields far beyond experimentally accessible scales. Our results indicate that random matrix universality provides a general framework for organizing ab initio predictions of interacting electron spectra in complex systems.

Comments
8 pages, 8 figures

Related papers

Spectral crossovers and universality in quantum spin chains coupled to random fields

Debojyoti Kundu, Santosh Kumar, Subhra Sen Gupta

We study the spectral properties of and spectral crossovers between different random matrix ensembles [Poissonian, Gaussian orthogonal ensemble (GOE), Gaussian unitary ensemble (GUE)] in correlated spin-chain systems, in the presence of random magnetic fields, and the scalar spin-chirality term, competing with the usual isotropic and time-reversal invariant Heisenberg term. We have investigated these crossovers in the context of the level-spacing distribution and the level-spacing ratio distribution. We use random matrix theory (RMT) analytical results to fit the observed Poissonian-to-GOE and GOE-to-GUE crossovers, and examine the relationship between the RMT crossover parameter $\ensuremath{\lambda}$ and scaled physical parameters of the spin-chain systems in terms of a scaling exponent. We find that the crossover behavior exhibits universality, in the sense that, it becomes independent of lattice size in the large Hamiltonian matrix dimension limit. Moreover, the scaling exponent obtained from such a finite size scaling analysis, seems to be quite robust and independent of the type of crossover considered or the specific spectral correlation measure used.

arXiv:2309.14076•Physical review. B./Physical review. B•Jan 21, 2022•10 citations

New electron correlation theories for transition metal chemistry

Konrad Heinrich Marti, Markus Reiher

Electronic structure theory faces many computational challenges in transition metal chemistry. Usually, density functional theory is the method of choice for theoretical studies on transition metal complexes and clusters mostly because it is the only feasible one, although its results are not systematically improvable. By contrast, multireference ab initio methods could provide a correct description of the electronic structure, but are limited to small molecules because of the tremendous computational resources required. In recent years, conceptually new ab initio methods emerged that turned out to be promising for theoretical coordination chemistry. We review and discuss two efficient parametrization schemes for the electronic wave function, the matrix product states and the complete-graph tensor network states. Their advantages are demonstrated at example transition metal complexes. Especially, tensor network states might provide the key to accurately describe strongly correlated and magnetic molecular systems in transition metal chemistry.

Physical Chemistry Chemical Physics•Jan 1, 2011•130 citations

Universal random matrix behavior of a Fermionic quantum gas

Maxime Dixmerias, Giuseppe Del Vecchio Del Vecchio, Cyprien Daix +6 more

Since its initial use by Wigner in describing heavy atom spectra, random matrix theory (RMT) has found applications and revealed universal laws in diverse physical contexts, from quantum field theory to disordered systems and wireless communications. A particularly compelling application arises in the mathematical structure of the many-body wavefunction of non-interacting Fermi gases, which underpins a complex spatial organization driven by Pauli’s exclusion principle. However, experimental validation of the counting statistics predicted in such systems has remained elusive. Here, we probe at the single-atom level ultracold atomic Fermi gases made of two interacting spin states, obtaining direct access to their counting statistics in situ. We show that, while the system is strongly attractive, each spin component is described to a high accuracy by RMT predictions based on Fredholm determinants. Our results constitute an experimental validation of the Fermi-sphere point process through the lens of RMT, and establish its relevance for strongly-interacting systems. Random matrix theory (RMT) is used to describe non-interacting ultracold Fermi gases. Here, the authors directly probe the full counting statistics in a 2D system of 6Li atoms with two interacting spin states, by means of a continuum quantum gas microscopy technique. The measured number and spacing statistics agree well with predictions from RMT, also in the strongly interacting regime.

arXiv:2510.25735•Nature Communications•Oct 3, 2026•0 citations

An ab-initio many-body method for electronic structure calculations of solids. I. Description of the method

I. Schnell, G. Czycholl, Robert C. Albers

We propose a new, alternative method for ab-initio calculations of the electronic structure of solids, which has been specifically adapted to treat many-body effects in a more rigorous way than many existing ab-initio methods. We start from a standard band-structure calculation for an effective one-particle Hamiltonian approximately describing the material of interest. This yields a suitable set of one-particle basis functions, from which well localized Wannier functions can be constructed using a method proposed by Marzari and Vanderbilt. Within this (minimal) basis of localized Wannier functions the matrix elements of the non-interacting (one-particle) Hamiltonian as well as the Coulomb matrix elements can be calculated. The result is a many-body Hamiltonian in second quantization with parameters determined from first principles calculations for the material of interest. The Hamiltonian is in the form of a multi-band Hamiltonian in second quantization (a kind of extended, multi-band Hubbard model) such that all the standard many-body methods can be applied. We explicitly show how this approach can be solved in the simplest many-body approximation, the mean-field Hartree-Fock approximation (HFA), which takes into account exact exchange and corrects for self-interaction effects.

arXiv:cond-mat/0304643•Apr 28, 2003•0 citations

Random matrix theory of charge distribution in disordered quantum impurity models

Maxime Debertolis, Serge Florens

We introduce a bare-bone random matrix quantum impurity model, by hybridizing a localized spinless electronic level with a bath of random fermions in the Gaussian Orthogonal Ensemble (GOE). While stripped out of correlations effects, this model reproduces some salient features of the impurity charge distribution obtained in previous works on interacting disordered impurity models. Computing by numerical sampling the impurity charge distribution in our model, we find a crossover from a Gaussian distribution (centered on half a charge unit) at large hybridization, to a bimodal distribution (centered both on zero and full occupations of the charge) at small hybridization. In the bimodal regime, a universal $(-3/2)$ power-law is also observed. All these findings are very well accounted for by an analytic surmise computed with a single random electron level in the bath. We also derive an exact functional integral for the general probability distribution function of eigenvalues and eigenstates, that formally captures the statistical behavior of our model for any number $N$ of fermionic orbitals in the bath. In the Gaussian regime and in the limit $N\to\infty$, we are able to solve exactly the random matrix theory (RMT) for the charge distribution, obtaining perfect agreement with the numerics. Our results could be tested experimentally in mesoscopic devices, for instance by coupling a small quantum dot to a chaotic electronic reservoir, and using a quantum point contact as local charge sensor for the quantum dot occupation.

arXiv:2507.22586•Jul 30, 2025•0 citations

Random matrices and quantum spin chains

Jonathan P. Keating, Noah Linden, H. J. Wells

Random matrix ensembles are introduced that respect the local tensor structure of Hamiltonians describing a chain of $n$ distinguishable spin-half particles with nearest-neighbour interactions. We prove a central limit theorem for the density of states when $n \rightarrow\infty$, giving explicit bounds on the rate of approach to the limit. Universality within a class of probability measures and the extension to more general interaction geometries are established. The level spacing distributions of the Gaussian Orthogonal, Unitary and Symplectic Ensembles are observed numerically for the energy levels in these ensembles.

arXiv:1403.1114•Mar 5, 2014•12 citations
We use ab initio electronic-structure methods to investigate random-matrix theory (RMT) universality in molecular electronic structure. Using single-reference electronic structure methods, including Hartree-Fock, configuration-interaction singles (CIS), density functional theory, and linear-response time-dependent density-functional theory, we compute single-particle orbital energies and many-electron excitations of several representative molecules (benzene, alanine, 1-phenylethylamine, methyloxirane, and helicene chains). For generic low-symmetry geometries, the unfolded spectra of these ab initio Hamiltonians exhibit Wigner-Dyson level statistics of the Gaussian orthogonal ensemble (GOE). For extended helicene chains we explicitly restrict to bound valence excitations below the ionization threshold and still observe GOE statistics, indicating that the RMT universality is present for physical states of direct relevance to real molecules. We further explore the electric and magnetic field dependence of the molecular electronic spectra. The variance of electric polarizability (level curvature K) is predicted to be non-analytic in the magnetic field which serves as an infrared cutoff, <K^2> proportional to log(1/|B|). We observe a transition to the Gaussian unitary ensemble (GUE) by increasing the magnetic fields, although it occurs only at magnetic fields far beyond experimentally accessible scales. Our results indicate that random matrix universality provides a general framework for organizing ab initio predictions of interacting electron spectra in complex systems.
We study the spectral properties of and spectral crossovers between different random matrix ensembles [Poissonian, Gaussian orthogonal ensemble (GOE), Gaussian unitary ensemble (GUE)] in correlated spin-chain systems, in the presence of random magnetic fields, and the scalar spin-chirality term, competing with the usual isotropic and time-reversal invariant Heisenberg term. We have investigated these crossovers in the context of the level-spacing distribution and the level-spacing ratio distribution. We use random matrix theory (RMT) analytical results to fit the observed Poissonian-to-GOE and GOE-to-GUE crossovers, and examine the relationship between the RMT crossover parameter $\ensuremath{\lambda}$ and scaled physical parameters of the spin-chain systems in terms of a scaling exponent. We find that the crossover behavior exhibits universality, in the sense that, it becomes independent of lattice size in the large Hamiltonian matrix dimension limit. Moreover, the scaling exponent obtained from such a finite size scaling analysis, seems to be quite robust and independent of the type of crossover considered or the specific spectral correlation measure used.
Electronic structure theory faces many computational challenges in transition metal chemistry. Usually, density functional theory is the method of choice for theoretical studies on transition metal complexes and clusters mostly because it is the only feasible one, although its results are not systematically improvable. By contrast, multireference ab initio methods could provide a correct description of the electronic structure, but are limited to small molecules because of the tremendous computational resources required. In recent years, conceptually new ab initio methods emerged that turned out to be promising for theoretical coordination chemistry. We review and discuss two efficient parametrization schemes for the electronic wave function, the matrix product states and the complete-graph tensor network states. Their advantages are demonstrated at example transition metal complexes. Especially, tensor network states might provide the key to accurately describe strongly correlated and magnetic molecular systems in transition metal chemistry.
Since its initial use by Wigner in describing heavy atom spectra, random matrix theory (RMT) has found applications and revealed universal laws in diverse physical contexts, from quantum field theory to disordered systems and wireless communications. A particularly compelling application arises in the mathematical structure of the many-body wavefunction of non-interacting Fermi gases, which underpins a complex spatial organization driven by Pauli’s exclusion principle. However, experimental validation of the counting statistics predicted in such systems has remained elusive. Here, we probe at the single-atom level ultracold atomic Fermi gases made of two interacting spin states, obtaining direct access to their counting statistics in situ. We show that, while the system is strongly attractive, each spin component is described to a high accuracy by RMT predictions based on Fredholm determinants. Our results constitute an experimental validation of the Fermi-sphere point process through the lens of RMT, and establish its relevance for strongly-interacting systems. Random matrix theory (RMT) is used to describe non-interacting ultracold Fermi gases. Here, the authors directly probe the full counting statistics in a 2D system of 6Li atoms with two interacting spin states, by means of a continuum quantum gas microscopy technique. The measured number and spacing statistics agree well with predictions from RMT, also in the strongly interacting regime.
We propose a new, alternative method for ab-initio calculations of the electronic structure of solids, which has been specifically adapted to treat many-body effects in a more rigorous way than many existing ab-initio methods. We start from a standard band-structure calculation for an effective one-particle Hamiltonian approximately describing the material of interest. This yields a suitable set of one-particle basis functions, from which well localized Wannier functions can be constructed using a method proposed by Marzari and Vanderbilt. Within this (minimal) basis of localized Wannier functions the matrix elements of the non-interacting (one-particle) Hamiltonian as well as the Coulomb matrix elements can be calculated. The result is a many-body Hamiltonian in second quantization with parameters determined from first principles calculations for the material of interest. The Hamiltonian is in the form of a multi-band Hamiltonian in second quantization (a kind of extended, multi-band Hubbard model) such that all the standard many-body methods can be applied. We explicitly show how this approach can be solved in the simplest many-body approximation, the mean-field Hartree-Fock approximation (HFA), which takes into account exact exchange and corrects for self-interaction effects.
We introduce a bare-bone random matrix quantum impurity model, by hybridizing a localized spinless electronic level with a bath of random fermions in the Gaussian Orthogonal Ensemble (GOE). While stripped out of correlations effects, this model reproduces some salient features of the impurity charge distribution obtained in previous works on interacting disordered impurity models. Computing by numerical sampling the impurity charge distribution in our model, we find a crossover from a Gaussian distribution (centered on half a charge unit) at large hybridization, to a bimodal distribution (centered both on zero and full occupations of the charge) at small hybridization. In the bimodal regime, a universal (−3/2)(-3/2)(−3/2) power-law is also observed. All these findings are very well accounted for by an analytic surmise computed with a single random electron level in the bath. We also derive an exact functional integral for the general probability distribution function of eigenvalues and eigenstates, that formally captures the statistical behavior of our model for any number NNN of fermionic orbitals in the bath. In the Gaussian regime and in the limit N→∞N\to\inftyN→∞, we are able to solve exactly the random matrix theory (RMT) for the charge distribution, obtaining perfect agreement with the numerics. Our results could be tested experimentally in mesoscopic devices, for instance by coupling a small quantum dot to a chaotic electronic reservoir, and using a quantum point contact as local charge sensor for the quantum dot occupation.
Random matrix ensembles are introduced that respect the local tensor structure of Hamiltonians describing a chain of nnn distinguishable spin-half particles with nearest-neighbour interactions. We prove a central limit theorem for the density of states when n→∞n \rightarrow\inftyn→∞, giving explicit bounds on the rate of approach to the limit. Universality within a class of probability measures and the extension to more general interaction geometries are established. The level spacing distributions of the Gaussian Orthogonal, Unitary and Symplectic Ensembles are observed numerically for the energy levels in these ensembles.