Configuration Interaction Wavefunctions Research Articles

The anion photoelectron spectrum and diabatization of tetrazolyl.

The potential energy surface of tetrazolyl [cyclic (N4CH)] has a conical intersection seam between the two lowest-energy electronic states near the ground state minimum geometry. This work treats that molecule. The potential energy surfaces used in this study are based on a least-squares fitting procedure that includes abinitio energies, energy gradients, and derivative couplings described using polynomials up to fourth-order and abinitio data obtained from multireference configuration interaction wave functions. A five-electronic-state description was generated with a root mean square absolute energy error of 9.6cm-1, compared to 326.8cm-1 when only second-order terms were used. The time-independent multimode vibronic coupling in the KDC approximation was used to simulate and analyze the anion ultraviolet photoelectron spectrum of tetrazolide.

X marks the spot: Accurate energies from intersecting extrapolations of continuum quantum Monte Carlo data.

We explore the application of an extrapolative method that yields very accurate total and relative energies from variational and diffusion quantum Monte Carlo (VMC and DMC) results. For a trial wave function consisting of a small configuration interaction (CI) wave function obtained from full CI quantum Monte Carlo and reoptimized in the presence of a Jastrow factor and an optional backflow transformation, we find that the VMC and DMC energies are smooth functions of the sum of the squared coefficients of the initial CI wave function and that quadratic extrapolations of the non-backflow VMC and backflow DMC energies intersect within uncertainty of the exact total energy. With adequate statistical treatment of quasi-random fluctuations, the extrapolate and intersect with polynomials of order two method is shown to yield results in agreement with benchmark-quality total and relative energies for the C2, N2, CO2, and H2O molecules, as well as for the C2 molecule in its first electronic singlet excited state, using only small CI expansion sizes.

Vibrational ADAPT-VQE: Critical points lead to problematic convergence.

Quantum chemistry is one of the most promising applications for which quantum computing is expected to have a significant impact. Despite considerable research in the field of electronic structure, calculating the vibrational properties of molecules on quantum computers remains a relatively unexplored field. In this work, we develop a vibrational Adaptive Derivative-Assembled Pseudo-Trotter Variational Quantum Eigensolver (vADAPT-VQE) formalism based on an infinite product representation (IPR) of anti-Hermitian excitation operators of the Full Vibrational Configuration Interaction (FVCI) wavefunction, which allows for preparing eigenstates of vibrational Hamiltonians on quantum computers. In order to establish the vADAPT-VQE algorithm using the IPR, we study the exactness of disentangled Unitary Vibrational Coupled Cluster (dUVCC) theory and show that dUVCC can formally represent the FVCI wavefunction in an infinite expansion. To investigate the performance of the vADAPT-VQE algorithm, we numerically study whether the vADAPT-VQE algorithm generates a sequence of operators that may represent the FVCI wavefunction. Our numerical results indicate frequent appearance of critical points in the wavefunction preparation using vADAPT-VQE. These results imply that one may encounter diminishing usefulness when preparing vibrational wavefunctions on quantum computers using vADAPT-VQE and that additional studies are required to find methods that can circumvent this behavior.

Reasons Why Most Single-Reference Coupled Cluster Methods Fail to Provide the Correct Adiabatic Potentials of a Diatomic Carbon Molecule: UCCSDecCCSD Potential Study.

Many single-reference coupled cluster (CC) methods offer adiabatically incorrect potentials when calculating the diatomic carbon molecule, so this problem has been studied extensively. Analysis of the full configuration interaction (FCI) wave function indicates that the main cause of the adiabatic collapse of potentials calculated by the CC method with singles, doubles, and triples (CCSDT) is the strongly increasing bonding character of the T4FCI cluster contribution. In turn, comparative analysis of the CCSDTQ adiabats X1Σg+ and B'1Σg+ demonstrates that the gap between them near the avoided crossing geometry is significantly reduced by quantitatively differentiating the character of the T4 and cluster contributions. These observations clearly indicate the need to take into account the T4 cluster contribution in the standard CC wave function to obtain the correct adiabatic potential. Further analysis of this issue shows that the T4 contribution must be additionally bonding to ensure the adiabatic correctness of the potential. What also seems very interesting is that when the UCCSDecCCSD method [Toboła, Chem. Phys. Lett. 2014, 614, 82-88] is used for the potential calculation, the shape of the potential is entirely determined by a subset of unrestricted Hartree-Fock (UHF) configurations, which are structurally identical to the ground-state configuration in the UHF-based CCSD wave function.

Approximate Excited-State Geometry Optimization with the State-Averaged Adaptive Sampling Configuration Interaction Algorithm with Large Active Spaces.

The selected configuration interaction (SCI) wave function is a useful approximation to the full configuration interaction (FCI) one. The adaptive sampling CI (ASCI) method is a deterministic SCI method. By combining ASCI and orbital optimization, the ASCI self-consistent field (ASCI-SCF) method, which is an approximation of the complete active space self-consistent field (CASSCF) method, can be formulated as well. However, their applicability has been tested mainly on the systems in their electronically ground states. In this work, we implement the state-average (SA) ansatz in ASCI-SCF calculations to calculate excited states. We also derive expressions for the approximate analytical gradient and implement them as a computer program. We demonstrate the applicability of the current method for calculating vertical and adiabatic excitation energies and optimizing the molecular geometries of thermally activated delayed fluorescence (TADF) molecules.

State-Interaction Approach for Evaluating g-Tensors within EOM-CC and RAS-CI Frameworks: Theory and Benchmarks.

Among various techniques designed for studying open-shell species, electron paramagnetic resonance (EPR) spectroscopy plays an important role. The key quantity measured by EPR is the g-tensor, describing the coupling between an external magnetic field and molecular electronic spin. One theoretical framework for quantum chemistry calculations of g-tensors is based on response theory, which involves substantial developments that are specific to the underlying electronic structure models. A simplified and easier-to-implement approach is based on the state-interaction scheme, in which perturbation is included by considering a small number of states. We describe and benchmark the state-interaction approach using equation-of-motion coupled-cluster and restricted-active-space configuration interaction wave functions. The analysis confirms that this approach can deliver accurate results and highlights caveats of applying it, such as a choice of the reference state, convergence with respect to the number of states used in calculations, etc. The analysis also contributes toward a better understanding of challenges in calculations of higher-order properties using approximate wave functions.

Toward a Unified Analytical Description of Internal Conversion and Intersystem Crossing in the Photodissociation of Thioformaldehyde. I. Diabatic Singlet States.

The photodissociation of thioformaldehyde is an archetypal system for the study of competition between internal conversion and intersystem crossing, which involves its two singlet states (S0 and S1) and two triplet states (T1 and T2). In order to perform accurate dynamic simulations, either quantum or quasi-classical, it is essential to construct an analytical representation for all necessary electronic structure data. In this work, a diabatic potential energy matrix (DPEM), Hd, for the two singlet states (S0 and S1) is reported. The analytical form of DPEM is symmetrized and constructed to reproduce adiabatic energies, energy gradients, and derivative couplings obtained from high-level multireference configuration interaction wave functions. The Hd is fully saturated in the molecular configuration space with a trajectory-guided point sampling approach. This Hd can provide the accurate description of the photodissociation of thioformaldehyde on its singlet states and is also a necessary part for incorporating the spin-orbit couplings into a unified diabatic framework. Preliminary quasi-classical trajectory simulations show that a roaming mechanism also exists in the molecular dissociation channel of thioformaldehyde.

Basis-set correction based on density-functional theory: Linear-response formalism for excited-state energies.

The basis-set correction method based on density-functional theory consists in correcting the energy calculated by a wave-function method with a given basis set by a density functional. This basis-set correction density functional incorporates the short-range electron correlation effects missing in the basis set. This results in accelerated basis convergences of ground-state energies to the complete-basis-set limit. In this work, we extend the basis-set correction method to a linear-response formalism for calculating excited-state energies. We give the general linear-response equations as well as the more specific equations for configuration-interaction wave functions. As a proof of concept, we apply this approach to the calculations of excited-state energies in a one-dimensional two-electron model system with harmonic potential and a Dirac-delta electron-electron interaction. The results obtained with full-configuration-interaction wave functions expanded in a basis of Hermite functions and a local-density-approximation basis-set correction functional show that the present approach does not help in accelerating the basis convergence of excitation energies. However, we show that it significantly accelerates basis convergences of excited-state total energies.

New analysis of the [formula omitted]C[formula omitted]O[formula omitted] (B[formula omitted] - X[formula omitted]) system: Spin-orbit and spin-rotation coupling of the X[formula omitted] state

In the present work a new experimental and theoretical analysis of the B2Σ+→ X2Σ+ system of the molecular ion 12C16O+ is performed. New transitions regarding the vibrational levels v′=4 of the B2Σ+ electronic state and the vibrational level v″=7 of the electronic state X2Σ+ have been recorded. For rationalising the experimental observations, molecular structure calculations were carried out and, from them, a detailed investigation about the fine structure of rotational levels of the X2Σ+ could be performed. For such, the spin-rotational constant, γ, is characterised through the Δg⊥ calculation, the perpendicular component of the electronic g-tensor, in combination with Curl’s relation. At equilibrium geometry, the present Δg⊥ is computed using the multireference configuration interaction wavefunction to be −2430 ppm in agreement with the experimental one [−2344 ppm]. The R-dependence of the g-tensor has been explored in order to estimate the theoretical γv (v=0–7). In addition, the importance of the lowest Π states in this kind of calculation is widely discussed. A comparison between experiment and theory is presented, validating our findings and the methodology employed in our analysis.

Toward Compact Selected Configuration Interaction Wave Functions with Quantum Monte Carlo─A Case Study of C2

The 1Σg+ ground state of C2 is investigated using truncated CIPSI-Jastrow CSF wave functions with Hartree-Fock orbitals within the framework of variational and diffusion quantum Monte Carlo. The truncation is performed based on the absolute value of the CI coefficients, and the Jastrow, molecular orbitals, and CI parameters are either partially or fully reoptimized with respect to the variational energy. Excellent absolute as well as bond dissociation energies are obtained at DMC level with very compact, fully optimized wave functions. By studying the expansions in more detail, we observe a change in the CI picture when reoptimizing the antisymmetric part of the CIPSI-Jastrow wave functions. Furthermore, we demonstrate that a decrease in the VMC energy as well as an improvement of the nodal surface quality can be achieved─with the same expansion size─if the CSFs are selected in the presence of a Jastrow correlation function, laying the foundation for a Jastrow selected CI scheme with quantum Monte Carlo.

Triaxiality and the nature of low-energy excitations in Ge76

The deformation properties of the low-lying states in Ge76 have been investigated following a safe-energy Coulomb excitation measurement with the GRETINA tracking array and CHICO2 heavy-ion counter at the ATLAS accelerator facility at Argonne National Laboratory. A comprehensive set of transition and static E2 matrix elements were extracted from the measured differential Coulomb cross sections and compared with results of configuration-interaction shell-model calculations and computations carried out within the framework of the generalized triaxial rotor model. The remarkable agreement between the calculated and experimental data supports a near-maximum triaxial deformation for the ground state of Ge76. In addition, the degree of softness of the asymmetry in Ge76 and Se76 was investigated using rotational invariants generated from configuration-interaction shell-model wave functions computed with the jj44b and JUN45 effective interactions. The resulting invariants are shown to be consistent with a stiff triaxial deformation in Ge76 and a predominantly soft triaxial potential for Se76, in agreement with the conclusions of recent works by this collaboration.5 MoreReceived 27 January 2023Accepted 3 April 2023DOI:https://doi.org/10.1103/PhysRevC.107.044314©2023 American Physical SocietyPhysics Subject Headings (PhySH)Research AreasNuclear reactionsNuclear structure & decaysNucleon distributionProperties59 ≤ A ≤ 89TechniquesCollective modelsShell modelNuclear Physics

Suppressed electric quadrupole moment of thulium atomic clock states

A method for highly accurate calculations of atomic electric quadrupole moments (EQM) is presented, using relativistic general-excitation-rank configuration interaction wave functions based on Dirac spinors. Application to the clock transition states of the thulium atom employing up to full Quadruple excitations for the atomic wave function yields a final value of ${Q}_{zz}({^{2}F}_{7/2})=0.07\begin{array}{c}+0.07\\ \ensuremath{-}0.00\end{array}$ a.u., establishing that the thulium electronic ground state has an exceptionally small EQM. A detailed analysis of this result is presented which has implications for EQMs of other atoms with unpaired $f$ electrons.

Energy natural orbital characterization of nonadiabatic electron wavepackets in the densely quasi-degenerate electronic state manifold.

Dynamics and energetic structure of largely fluctuating nonadiabatic electron wavepackets are studied in terms of Energy Natural Orbitals (ENOs) [K. Takatsuka and Y. Arasaki, J. Chem. Phys. 154, 094103 (2021)]. Such huge fluctuating states are sampled from the highly excited states of clusters of 12 boron atoms (B12), which have densely quasi-degenerate electronic excited-state manifold, each adiabatic state of which gets promptly mixed with other states through the frequent and enduring nonadiabatic interactions within the manifold. Yet, the wavepacket states are expected to be of very long lifetimes. This excited-state electronic wavepacket dynamics is extremely interesting but very hard to analyze since they are usually represented in large time-dependent configuration interaction wavefunctions and/or in some other complicated forms. We have found that ENO gives an invariant energy orbital picture to characterize not only the static highly correlated electronic wavefunctions but also those time-dependent electronic wavefunctions. Hence, we first demonstrate how the ENO representation works for some general cases, choosing proton transfer in water dimer and electron-deficient multicenter chemical bonding in diborane in the ground state. We then penetrate with ENO deep into the analysis of the essential nature of nonadiabatic electron wavepacket dynamics in the excited states and show the mechanism of the coexistence of huge electronic fluctuation and rather strong chemical bonds under very random electron flows within the molecule. To quantify the intra-molecular energy flow associated with the huge electronic-state fluctuation, we define and numerically demonstrate what we call the electronic energy flux.

Analytic Gradients for Selected Configuration Interaction

We develop analytic gradients for selected configuration interaction wave functions. Despite all pairs of molecular orbitals now potentially having to be considered for the coupled perturbed Hartree-Fock equations, we show that degenerate orbital pairs belonging to different irreducible representations in the largest abelian subgroup do not need to be included and instabilities due to degeneracies are avoided. We introduce seminumerical gradients and use them to validate the analytic approach even when near degeneracies are present due to high-symmetry geometries being slightly distorted to break symmetry. The method is applied to carbon monoxide, ammonia, square planar H4, hexagonal planar H6, and methane for a range of bond lengths where we demonstrate that analytic gradients for selected configuration interaction can approach the quality of full configuration interaction yet only use a very small fraction of its determinants.

A truncated Davidson method for the efficient "chemically accurate" calculation of full configuration interaction wavefunctions without any large matrix diagonalization.

This work develops and illustrates a new method of calculating "chemically accurate" electronic wavefunctions (and energies) via a truncated full configuration interaction (CI) procedure, which arguably circumvents the large matrix diagonalization that is the core problem of full CI and is also central to modern selective CI approaches. This is accomplished simply by following the standard/ubiquitous Davidson method in its "direct" form-wherein, in each iteration, the electronic Hamiltonian operator is applied directly in second quantization to the Ritz vector/wavefunction from the prior iteration-except that (in this work) only a small portion of the resultant expansion vector is actually even computed (through the application of only a similarly small portion of the Hamiltonian). Specifically, at each iteration of this truncated Davidson approach, the new expansion vector is taken to be twice as large as that from the prior iteration. In this manner, a small set of highly truncated expansion vectors (say 10-30) of increasing precision is incrementally constructed, forming a small subspace within which diagonalization of the Hamiltonian yields clear, consistent, and monotonically variational convergence to the approximate full CI limit. The good efficiency in which convergence to the level of chemical accuracy (1.6 mhartree) is achieved suggests, at least for the demonstrated problem sizes-Hilbert spaces of 1018 and wavefunctions of 108 determinants-that this truncated Davidson methodology can serve as a replacement of standard CI and complete-active space approaches in circumstances where only a few chemically significant digits of accuracy are required and/or meaningful in view of ever-present basis set limitations.

Quantification of electron correlation for approximate quantum calculations.

State-of-the-art many-body wave function techniques rely on heuristics to achieve high accuracy at an attainable computational cost to solve the many-body Schrödinger equation. By far, the most common property used to assess accuracy has been the total energy; however, total energies do not give a complete picture of electron correlation. In this work, we assess the von Neumann entropy of the one-particle reduced density matrix (1-RDM) to compare selected configuration interaction (CI), coupled cluster, variational Monte Carlo, and fixed-node diffusion Monte Carlo for benchmark hydrogen chains. A new algorithm, the circle reject method, is presented, which improves the efficiency of evaluating the von Neumann entropy using quantum Monte Carlo by several orders of magnitude. The von Neumann entropy of the 1-RDM and the eigenvalues of the 1-RDM are shown to distinguish between the dynamic correlation introduced by the Jastrow and the static correlation introduced by determinants with large weights, confirming some of the lore in the field concerning the difference between the selected CI and Slater-Jastrow wave functions.

Active Spaces and Non-Orthogonal Configuration Interaction Approaches for Investigating Molecules on Metal Surfaces.

We test a set of multiconfigurational wavefunction approaches for calculating the ground state electron population for a two-site Anderson model representing a molecule on a metal surface. In particular, we compare (i) a Hartree Fock like wavefunction where frontier orbitals are allowed to be nonorthogonal versus (ii) a fully non-orthogonal configuration interaction wavefunction based on constrained Hartree-Fock states. We test both the strong and weak metal-molecule hybridization (Γ) limits as well as the strong and weak electron-electron repulsion (U) limits. We obtain accurate results as compared with exact numerical renormalization group theory, recovering charge transfer states where appropriate. The current framework should open a path to run molecular non-adiabatic dynamics on metal surfaces.

Efficient Computation of Two-Electron Reduced Density Matrices via Selected Configuration Interaction.

We create an approach to efficiently calculate two-electron reduced density matrices (2-RDMs) using selected configuration interaction wavefunctions. This is demonstrated using the specific example of Monte Carlo configuration interaction (MCCI). The computation of the 2-RDMs is accelerated by using ideas from fast implementations of full configuration interaction (FCI) and recent advances in implementing the Slater-Condon rules using hardware bitwise operations. This method enables a comparison of MCCI and truncated CI 2-RDMs with FCI values for a range of molecules, which includes stretched bonds and excited states. The accuracy in energies, wavefunctions, and 2-RDMs is seen to exhibit a similar behavior. We find that MCCI can reach sufficient accuracy of the 2-RDM using significantly fewer configurations than truncated CI, particularly for systems with strong multireference character.

Calculation of absolute Raman scattering cross-sections using vibrational self-consistent field/vibrational configuration interaction wave functions.

In the present study, the differential scattering cross-sections, depolarization ratios and Raman shifts of small molecular systems are obtained from configuration iteration wave functions of vibrational self-consistent field (VSCF) states. The transition polarizabilities were modeled using the Placzek approximation, neglecting those contributions not arising from the electric dipole mechanism. This theoretical approach is considered a good approximation for samples that absorb in the UV range if the excitation radiation falls in the visible region, as is the case of the molecules selected for the present study, namely: water, methane, and acetylene. Potential energy and electronic polarizability surfaces are calculated by the CCSD(T) and CC3 methods with aug-cc-p(C)V(T,Q,5)Z basis sets. The vibrational Hamiltonian includes the vibrational angular momentum contribution of the Watson kinetic energy operator. As expected, due to the variational nature of the VSCF and vibrational configuration interaction (VCI) methods, the Raman transition wavenumbers are substantially improved over the harmonic predictions. Surprisingly, the scattering cross-sections obtained using the harmonic approximation or the VSCF method better agrees with the experimental values than those cross-sections predicted using VCI wave functions. The more significant deviations of the VCI results from the experimental reference may be related to the significant uncertainties of the measured cross-sections. Still, it may also indicate that the VCI Raman transition moments may require a more accurate description of the electronic polarizability surface. Finally, the depolarization ratios calculated for H2 O and C2 D2 using harmonic and VCI wave functions have similar accuracy, whereas, for C2 H2 and C2 HD, the VCI results are more accurate.

Nature of chemical bond and potential barrier in an invariant energy-orbital picture.

Physical nature of the chemical bond and potential barrier is studied in terms of energy natural orbitals (ENOs), which are extracted from highly correlated electronic wavefunctions. ENO provides an objective one-electron picture about energy distribution in a molecule, just as the natural orbitals (NOs) represent one electron view about electronic charge distribution. ENO is invariant in the same sense as NO is, that is, ENOs converge to the exact ones as a series of approximate wavefunctions approach the exact one, no matter how the methods of approximation are adopted. Energy distribution analysis based on ENO can give novel insights about the nature of chemical bonding and formation of potential barriers, besides information based on the charge distribution alone. With ENOs extracted from full configuration interaction wavefunctions in a finite yet large enough basis set, we analyze the nature of chemical bonding of three low-lying electronic states of a hydrogen molecule, all being in different classes of the so-called covalent bond. The mechanism of energy lowering in bond formation, which gives a binding energy, is important, yet not the only concern for this small molecule. Another key notion in chemical bonding is whether a potential basin is well generated stiff enough to support a vibrational state(s) on it. Based on the virial theorem in the adiabatic approximation and in terms of the energy and force analyses with ENOs, we study the roles of the electronic kinetic energy and its nuclear derivative(s) on how they determine the curvature (or the force constant) of the potential basins. The same idea is applied to the potential barrier and, thereby, the transition states. The rate constant within the transition-state theory is formally shown to be described in terms of the electronic kinetic energy and the nuclear derivatives only. Thus, the chemical bonding and rate process are interconnected behind the scenes. Besides this aspect, we pay attention to (1) the effects of electron correlation that manifests itself not only in the orbital energy but also in the population of ENOs and (2) the role of nonadiabaticity (diabatic state mixing), resulting in double basins and a barrier on a single potential curve in bond formation. These factors differentiate a covalent bond into subclasses.