Multiconfigurational Self-consistent Field Wave Functions Research Articles

Potential-Energy Curves for the Ground and Several Electronic States of NdO and NdS.

Potential energy curves (PECs) were calculated for 21 and 18 electronic states of NdO and NdS molecules, respectively. In each case, static electron correlation effects were described by incomplete model space multiconfiguration self-consistent field wave functions based on an active space that included the most important valence orbitals. Dynamic electron correlation was included by the multireference second-order generalized Van Vleck perturbation theory method. Scalar-relativistic contributions were included by the effective core potential approach, using def2-TZVPP basis sets. Spin-dependent relativistic corrections were determined to be small and negligible for the Nd atom and so were not included in the calculations. The 21 and 18 electronic states of NdO and NdS were predicted to be in the excitation energy range of ∼3.2 and ∼2.7 eV, respectively. The ground electronic states of NdO and NdS were determined as 15H (6s4fσ4fϕ4fδ) and 15H (4fϕ4fπ4fπ6s), with spectroscopic constants: bond length Re = 1.780 and 2.325 Å, and harmonic frequency ωe = 891 and 538 cm-1, respectively.

Variational Pair-Density Functional Theory: Dealing with Strong Correlation at the Protein Scale.

Multiconfigurational pair-density functional theory (MC-PDFT) offers a promising solution to the challenges faced by traditional density functional theory (DFT) in addressing molecular systems containing transition metals, open-shells, or strong correlations in general. By utilizing both the density and on-top pair-density, MC-PDFT can make use of a more flexible multiconfigurational wave function to capture the necessary static correlation, while the pair-density functional also includes the effect of dynamic correlation. So far, MC-PDFT has been used after a multiconfigurational self-consistent field (MCSCF) step, using the orbitals and configuration interaction coefficients from the converged MCSCF wave function to compute PDFT energies and properties. Here, instead, we propose to perform a direct optimization of the wave function using the pair-density functionals, resulting in a variational formulation of MC-PDFT. We derive the expressions for the wave function gradient and illustrate their similarity to standard MCSCF equations. Furthermore, we illustrate the accuracy on a set of singlet-triplet gaps as well as dissociation curves. Our findings highlight one of MC-PDFT's standout features: a reduced dependency on the active space size compared to conventional multiconfigurational wave function methodologies. Additionally, we show that the computational cost of MC-PDFT is potentially lower than MCSCF and often on-par with standard Kohn-Sham DFT, which is demonstrated by performing a MC-PDFT calculation of the entire ferredoxin protein with 1447 atoms and nearly 12000 basis functions.

Complex Linear Response Functions for a Multiconfigurational Self-Consistent Field Wave Function in a High Performance Computing Environment.

We present novel developments for the highly efficient evaluation of complex linear response functions of a multiconfigurational self-consistent field (MCSCF) wave function as implemented in MultiPsi. Specifically, expressions for the direct evaluation of linear response properties at given frequencies using the complex polarization propagator (CPP) approach have been implemented, within both the Tamm-Dancoff approximation (TDA) and the random phase approximation (RPA). Purely real algebra with symmetric and antisymmetric trial vectors in a shared subspace is used wherein the linear response equations are solved. Two bottlenecks of large scale MC-CPP calculations, namely, the memory footprint and computational time, are addressed. The former is addressed by limiting the size of the subspace of trial vectors by using singular value decomposition (SVD) on either orbital or CI subspaces. The latter is addressed using an efficient parallel implementation as well as the strategy of dynamically adding linear response equations at near-convergence to neighboring roots. Furthermore, a novel methodology for decomposing MC-CPP spectra in terms of intuitive orbital excitations in an approximate fashion is presented. The performance of the code is illustrated with several numerical examples, including the X-ray spectrum of a molecule with nearly one hundred atoms. Additionally, for X-ray spectroscopy, the effect of including or excluding the core orbital in the active space on small covalent metal complexes is discussed.

DENSITY FUNCTIONAL AND GREEN’S FUNCTIONS METHOD TO COMPUTING SPECTRAL PARAMETERS OF DIATOMIC MOLECULES

It is presented a new effective method of calculating the energy and spectral parameters of diatomic molecules based on the hybrid theory of the quasi-particle density functional and the theory of Green's functions. As an illustration, the data of the calculation of the vertical ionization potentials and the coupling constants (vibrational structure) of the photoelectron spectra of a number of diatomic molecules, in particular, N2, are received. It is presented a detailed comparison of the received results with the data of standard theories of the Hartree-Fock type, the multi-configuration electron propagator method, and the extended theory based on Koopmans' theorem using multi-configurational self-consistent field wave functions with different sets of basis functions. Iit is shown that the consistent, maximally precise consideration of exchange-correlation effects and reorganization effects within the framework of the combined theory leads to a rather significant improvement in the agreement of theoretical and experimental data both in terms of ionization potentials and photoelectron spectra in general.

Localized Active Space Pair-Density Functional Theory

Accurate quantum chemical methods for the prediction of spin-state energy gaps for strongly correlated systems are computationally expensive and scale poorly with the size of the system. This makes calculations for many experimentally interesting molecules impractical even with abundant computational resources. Previous work has shown that the localized active space (LAS) self-consistent field (SCF) method can be an efficient way to obtain multiconfiguration SCF wave functions of comparable quality to the corresponding complete active space (CAS) ones. To obtain quantitative results, a post-SCF method is needed to estimate the complete correlation energy. One such method is multiconfiguration pair-density functional theory (PDFT), which calculates the energy based on the density and on-top pair density obtained from a multiconfiguration wave function. In this work, we introduce localized-active-space PDFT, which uses a LAS wave function for subsequent PDFT calculations. The method is tested by computing spin-state energies and gaps in conjugated organic molecules and a bimetallic compound and comparing to the corresponding CAS-PDFT values.

How Much Dispersion Energy Is Included in the Multiconfigurational Interaction Energy?

We demonstrate how to quantify the amount of dispersion interaction recovered by supermolecular calculations with the multiconfigurational self-consistent field (MCSCF) wave functions. For this purpose, we present a rigorous derivation which connects the portion of dispersion interaction captured by the assumed wave function model—the residual dispersion interaction—with the size of the active space. Based on the obtained expression for the residual dispersion contribution, we propose a dispersion correction for the MCSCF that avoids correlation double counting. Numerical demonstration for model four-electron dimers in both ground and excited states described with the complete active space self-consistent field (CASSCF) reference serves as a proof-of-concept for the method. Accurate results, largely independent of the size of the active space, are obtained. For many-electron systems, routine CASSCF interaction energy calculations recover a tiny fraction of the full second-order dispersion energy. We found that the residual dispersion is non-negligible only for purely dispersion-bound complexes.

Why is Si2H2 Not Linear? An Intrinsic Quasi-Atomic Bonding Analysis.

The molecular energy of Si2H2 geometric structures increases in the order dibridged < trans-bent < linear, in contrast to acetylene, C2H2, for which the linear structure is the global minimum. In this study, the intra-atomic (antibonding) and bonding contributions to the total molecular energy of these valence isoelectronic molecules are computed by expressing the density matrices of the full valence space multiconfiguration self-consistent field wave function in terms of quasi-atomic orbitals. The analysis shows that the intra-atomic contributions to the molecular energy become less favorable in the order dibridged → trans-bent → linear for both C2H2 and Si2H2. By contrast, the inter-atomic bonding contributions become energetically more favorable in that order for both C2H2 and Si2H2. The two systems differ as follows. For Si2H2, the antibonding intra-atomic energy changes that occur when the dibridged molecule reconstructs into the trans-bent and linear structures prevail over the interatomic interactions that induce bond formation. In contrast, for C2H2, the interatomic interactions that create bonds prevail over the intra-atomic energy changes that occur when the dibridged molecule reconstructs into the trans-bent and linear structures. The intra-atomic energy changes that occur in these systems are related to the hybridization of the heavy atoms in an analogous manner to the hybridization of C in CH4 from (2s)2(2p)2 to sp3 hybrid orbitals.

An Electron Propagator Approach Based on a Multiconfigurational Reference State for the Investigation of Negative-Ion Resonances Using a Complex Absorbing Potential Method.

Negative-ion resonances are important metastable states that result from the collision between an electron and a neutral target. The course of many chemical processes in nature is often dictated by how an intermediate resonance state falls apart. This article reports on the development of an electron propagator (EP) based on a Hamiltonian Ĥ perturbed by a complex absorbing potential (CAP) and a multiconfigurational self-consistent field (MCSCF) initial state to study these resonances. Perturbation of Ĥ by a CAP makes the resonances amenable to a bound-state method like MCSCF. Resonances stand out among the non-resonant states as persistent complex eigenvalues of the perturbed Ĥ when the strength (η) of the CAP is varied. The MCSCF method gives a reliable and accurate description of the target states, especially when the non-dynamical correlations are dominant. The resonance energies are obtained from the poles of the EP. We propose three variants of our EP depending on how the effect of the CAP is introduced. We find that the computationally most efficient variant is the one in which the reference state of the EP is an unperturbed MCSCF wavefunction and a non-zero CAP is defined only on the virtual orbital subspace of the reference state. The onset of the CAP is carefully optimized in order to minimize the artifacts due to reflections from the CAP. An extrapolation method (based on a Padé approximant) and a de-perturbation method are adopted in order to account for the limitations of finite basis sets used and determine the resonance energy in the limit of η → 0. 2P Be-, 2Πg N2-, and 2Π CO- shape resonances are investigated. The position and width of these resonances computed in this study agree well with those reported earlier in the literature.

Correlation effects in B1s core-excited states of boronic-acid derivatives: An experimental and computational study.

We performed a theoretical investigation on the influence of electronic correlation effects on the B1s NEXAFS spectrum of boronic acid derivatives, namely, boric acid [B(OH)3], phenyl boronic acid (PBA), and 1,4-phenyl diboronic acid (PDBA), employing different computational schemes of increasing complexity, ranging from the purely one-electron scheme based on the transition potential method of density functional theory (DFT-TP), time-dependent DFT (TDDFT), and multiconfigurational self-consistent field (MCSCF). We also report experimental measurements of the B1s NEXAFS spectra of the aforementioned molecules together with the high-resolution C1s NEXAFS spectrum of PBA. We demonstrate that due to the shallow B1s core energy levels compared to C, O, and N, the inclusion of static correlation effects, which can be incorporated by using multireference approaches to excited states, assumes a decisive role in reconciling experiment and theory on B1s core-electron excitation energies and oscillator strengths to valence states. This claim is corroborated by the good agreement that we find between the DFT-TP calculated C1s NEXAFS spectrum and that experimentally measured for PBA and by the failure of both DFT-TP and TDDFT approaches with a selection of xc functionals kernels to properly describe the B1s NEXAFS spectrum of PBA and PDBA, at variance with the good agreement with the experiment that is found by employing the MCSCF wave function approach.

Exploration of H2 binding to the [NiFe]-hydrogenase active site with multiconfigurational density functional theory.

The combination of density functional theory (DFT) with a multiconfigurational wave function is an efficient way to include dynamical correlation in calculations with multiconfiguration self-consistent field wave functions. These methods can potentially be employed to elucidate reaction mechanisms in bio-inorganic chemistry, where many other methods become either too computationally expensive or too inaccurate. In this paper, a complete active space (CAS) short-range DFT (CAS-srDFT) hybrid was employed to investigate a bio-inorganic system, namely H2 binding to the active site of [NiFe] hydrogenase. This system was previously investigated with coupled-cluster (CC) and multiconfigurational methods in the form of cumulant-approximated second-order perturbation theory, based on the density matrix renormalization group (DMRG). We find that it is more favorable for H2 to bind to Ni than to Fe, in agreement with previous CC and DMRG calculations. The accuracy of CAS-srDFT is comparable to both CC and DMRG, despite much smaller active spaces were employed than in the corresponding DMRG calculations. This enhanced efficiency at the smaller active spaces shows that CAS-srDFT can become a useful method for bio-inorganic chemistry.

Multiconfigurational and DFT analyses of the electromeric formulation and UV–vis absorption spectra of the superoxide adduct of ferrous superoxide reductase

The putative initial adduct of ferrous superoxide reductase (SOR) with superoxide has been alternatively formulated as ferric-peroxo or ferrous-superoxo. The ~600-nm UV–vis absorption band proposed to be assigned to this adduct (either as sole intermediate in the SOR catalytic cycle, or as one of the two intermediates) has recently been interpreted as due to a ligand-to-metal charge transfer, involving thiolate and superoxide in a ferrous complex, contrary to an alternative assignment as a predominantly cysteine thiolate-to-ferric charge transfer in a ferric-peroxo electromer. In an attempt to clarify the electromeric formulation of this adduct, we report a computational study using a multiconfigurational complete active space self-consistent field (MC-CASSCF) wave function approach as well as modelling the UV–vis absorption spectra with time-dependent density functional theory (TD-DFT). The MC-CASSCF calculations disclose a weak interaction between iron and the dioxygenic ligand and a dominant configuration with an essentially ferrous-superoxo character. The computed UV–vis absorption spectra reveal a marked dependence on the choice of density functional – both in terms of location of bands and in terms of orbital contributors. For the main band in the visible region, besides the recently reported thiolate-to-superoxide charge transfer, a more salient, and less functional-dependent, feature is a thiolate-to-ferric iron charge transfer, consistent with a ferric-peroxo electromer. By contrast, the computed UV–vis spectra of a ferric-hydroperoxo SOR model match distinctly better (and with no qualitative dependence on the DFT methodology) the 600-nm band as due to a mainly thiolate-to-ferric character – supporting the assignment of the SOR “600-nm intermediate” as a S=5/2 ferric-hydroperoxo species.

Chemical bonding: the orthogonal valence-bond view.

Chemical bonding is the stabilization of a molecular system by charge- and spin-reorganization processes in chemical reactions. These processes are said to be local, because the number of atoms involved is very small. With multi-configurational self-consistent field (MCSCF) wave functions, these processes can be calculated, but the local information is hidden by the delocalized molecular orbitals (MO) used to construct the wave functions. The transformation of such wave functions into valence bond (VB) wave functions, which are based on localized orbitals, reveals the hidden information; this transformation is called a VB reading of MCSCF wave functions. The two-electron VB wave functions describing the Lewis electron pair that connects two atoms are frequently called covalent or neutral, suggesting that these wave functions describe an electronic situation where two electrons are never located at the same atom; such electronic situations and the wave functions describing them are called ionic. When the distance between two atoms decreases, however, every covalent VB wave function composed of non-orthogonal atomic orbitals changes its character from neutral to ionic. However, this change in the character of conventional VB wave functions is hidden by its mathematical form. Orthogonal VB wave functions composed of orthonormalized orbitals never change their character. When localized fragment orbitals are used instead of atomic orbitals, one can decide which local information is revealed and which remains hidden. In this paper, we analyze four chemical reactions by transforming the MCSCF wave functions into orthogonal VB wave functions; we show how the reactions are influenced by changing the atoms involved or by changing their local symmetry. Using orthogonal instead of non-orthogonal orbitals is not just a technical issue; it also changes the interpretation, revealing the properties of wave functions that remain otherwise undetected.

Ab initio study of the RbSr electronic structure: potential energy curves, transition dipole moments, and permanent electric dipole moments.

Excited states and the ground state of the diatomic molecule RbSr were calculated by post Hartree-Fock molecular orbital theory up to 22000 cm(-1). We applied a multireference configuration interaction calculation based on multiconfigurational self-consistent field wave functions. Both methods made use of effective core potentials and core polarization potentials. Potential energy curves, transition dipole moments, and permanent electric dipole moments were determined for RbSr and could be compared with other recent calculations. We found a good agreement with experimental spectra, which have been obtained recently by helium nanodroplet isolation spectroscopy. For the lowest two asymptotes (Rb (5s (2)S) + Sr (5s4d (3)P°) and Rb (5p (2)P°) + Sr (5s(2) (1)S)), which exhibit a significant spin-orbit coupling, we included relativistic effects by two approaches, one applying the Breit-Pauli Hamiltonian to the multireference configuration interaction wave functions, the other combining a spin-orbit Hamiltonian and multireference configuration interaction potential energy curves. Using the results for the relativistic potential energy curves that correspond to the Rb (5s (2)S) + Sr (5s4d (3)P°) asymptote, we have simulated dispersed fluorescence spectra as they were recently measured in our lab. The comparison with experimental data allows to benchmark both methods and demonstrate that spin-orbit coupling has to be included for the lowest states of RbSr.

Assessment of charge-transfer excitations with time-dependent, range-separated density functional theory based on long-range MP2 and multiconfigurational self-consistent field wave functions

Charge transfer excitations can be described within Time-Dependent Density Functional Theory (TD-DFT), not only by means of the Coulomb Attenuated Method (CAM) but also with a combination of wave function theory and TD-DFT based on range separation. The latter approach enables a rigorous formulation of multi-determinantal TD-DFT schemes where excitation classes, which are absent in conventional TD-DFT spectra (like for example double excitations), can be addressed. This paper investigates the combination of both the long-range Multi-Configuration Self-Consistent Field (MCSCF) and Second Order Polarization Propagator Approximation (SOPPA) ansätze with a short-range DFT (srDFT) description. We find that the combinations of SOPPA or MCSCF with TD-DFT yield better results than could be expected from the pure wave function schemes. For the Time-Dependent MCSCF short-range DFT ansatz (TD-MC-srDFT) excitation energies calculated over a larger benchmark set of molecules with predominantly single reference character yield good agreement with their reference values, and are in general comparable to the CAM-B3LYP functional. The SOPPA-srDFT scheme is tested for a subset of molecules used for benchmarking TD-MC-srDFT and performs slightly better against the reference data for this small subset. Beyond the proof-of-principle calculations comprising the first part of this contribution, we additionally studied the low-lying singlet excited states (S1 and S2) of the retinal chromophore. The chromophore displays multireference character in the ground state and both excited states exhibit considerable double excitation character, which in turn cannot be described within standard TD-DFT, due to the adiabatic approximation. However, a TD-MC-srDFT approach can account for the multireference character, and excitation energies are obtained with accuracy comparable to CASPT2, although using a much smaller active space.

Alternative separation of exchange and correlation energies in multi-configuration range-separated density-functional theory

The alternative separation of exchange and correlation energies proposed by Toulouse et al. [Theor. Chem. Acc. 114, 305 (2005)] is explored in the context of multi-configuration range-separated density-functional theory. The new decomposition of the short-range exchange-correlation energy relies on the auxiliary long-range interacting wavefunction rather than the Kohn-Sham (KS) determinant. The advantage, relative to the traditional KS decomposition, is that the wavefunction part of the energy is now computed with the regular (fully interacting) Hamiltonian. One potential drawback is that, because of double counting, the wavefunction used to compute the energy cannot be obtained by minimizing the energy expression with respect to the wavefunction parameters. The problem is overcome by using short-range optimized effective potentials (OEPs). The resulting combination of OEP techniques with wavefunction theory has been investigated in this work, at the Hartree-Fock (HF) and multi-configuration self-consistent-field (MCSCF) levels. In the HF case, an analytical expression for the energy gradient has been derived and implemented. Calculations have been performed within the short-range local density approximation on H2, N2, Li2, and H2O. Significant improvements in binding energies are obtained with the new decomposition of the short-range energy. The importance of optimizing the short-range OEP at the MCSCF level when static correlation becomes significant has also been demonstrated for H2, using a finite-difference gradient. The implementation of the analytical gradient for MCSCF wavefunctions is currently in progress.

On the electronic structure of the diazomethane molecule

The electronic structure and chemical bonding in the diazomethane molecule are investigated using full-valence generalized valence bond (GVB) methods. We point out that an ab initio-based bonding model must correspond directly to a wave function that yields at least qualitatively corrects values for the structural parameters of a molecule, that is, molecular geometry, vibrational frequencies, and dipole moment. However, in the case of diazomethane, when trying to emulate the bonding models proposed in the literature through full-valence GVB wave functions, we found out that all of them are directly associated with optimized molecular geometries that are saddle points in the molecular potential energy surface. This spurious behavior is corrected by a multiconfiguration–self-consistent field (MCSCF) wave function that incorporates an enlarged “pi-like” active space enabling a complete active space self-consistent field (CASSCF) block, with more active orbitals than electrons, together with a “sigma-like” generalized valence bond with restricted configuration interaction (GVB-RCI) block. With this wave function, we are able to generate the best calculated set of harmonic frequencies to date for the diazomethane molecule. The physical effects that are important for the correct description of its electronic and vibrational structure are then discussed using a series of MCSCF wave functions. This result leads to a decomposition of the electronic wave function into diabatic GVB-RCI chemical structures along the CH2 wagging mode illustrating the necessity to understand the chemical bonding in this molecule as a superposition of bonding patterns. Some structural properties of diazomethane and diazocompounds are then successfully analyzed using our model.

Potential curves for inner-shell states of CO calculated at multiconfigurational self-consistent field level

A general strategy to calculate potential curves at multiconfigurational self-consistent field (MCSCF) level for inner-shell states is reported in this paper. Convergence is commonly very tough for inner-shell states, especially at this level of calculation, due to the problem of variational collapse of the inner-shell wave function to the ground or to a low-lying excited state. The present method allows to avoid this drawback by a sequence of constrained optimization in the orbital mixing step. The specific states studied are that resulting from transitions X (1)Σ(+) → (C 1s(-1) π(∗)) (1,3)Π of CO. Accurate values are achieved for transition energies and vibrational splittings. A comparison is made with other approach, i.e., inner-shell CI based on a MCSCF wave function optimized for ground or low-lying excited states. This last approach is shown to fail in describing the whole potential curve.

Pathway analysis of super-exchange electronic couplings in electron transfer reactions using a multi-configuration self-consistent field method

We present a novel pathway analysis of super-exchange electronic couplings in electron transfer reactions using localized molecular orbitals from multi-configuration self-consistent field (MCSCF) calculations. In our analysis, the electronic coupling and the tunneling pathways can be calculated in terms of the configuration interaction (CI) Hamiltonian matrix obtained from the localized MCSCF wave function. Making use of the occupation restricted multiple active spaces (ORMAS) method can effectively produce the donor, acceptor, and intermediate configuration state functions (CSFs) and CIs among these CSFs. In order to express the electronic coupling as a sum of individual tunneling pathways contributions, we employed two perturbative methods: Löwdin projection-iteration method and higher-order super-exchange method. We applied them to anion couplings of butane-1,4-diyl and pentane-1,5-diyl. The results were (1) the electronic couplings calculated from the two perturbative methods were in reasonable agreement with those from a non-perturbative method (one-half value of the energy difference between the ground and first excited states), (2) the main tunneling pathways consisted of a small number of lower-order super-exchange pathways where bonding, anti-bonding, or extra-valence-shell orbitals were used once or twice, and (3) the interference among a huge number of higher-order super-exchange pathways significantly contributed to the overall electronic coupling, whereas each of them contributed only fractionally. Our method can adequately take into account both effects of non-dynamical electron correlation and orbital relaxation. Comparing with the analyses based on the Koopmans' theorem (ignoring both effects) and the ORMAS-CIs from frozen localized reference orbitals (ignoring the effect of orbital relaxation), we discuss these effects.

Communication: Rotational g-factor and spin-rotation constant of CH+

The rotational g-factor and spin-rotation constants of the methylidynium ion CH(+) have been calculated for the first time with a large multiconfigurational self-consistent field wave function and at the coupled-cluster singles and doubles level augmented by a perturbative triples correction. The results for an equilibrium internuclear distance as well as for the v=0, J=1 vibration-rotational state are presented.

ChemInform Abstract: Accurate ab initio Calculations of the Quadrupole Moment of Acetylene. A Combined Study of Basis Set, Correlation, and Vibrational Effects.

The quadrupole moment of acetylene has been studied at the multiconfiguration self‐consistent field (MCSCF) and multireference single and double configuration interaction (MRSDCI) level of theory. At the MCSCF level the π‐CI complete active space SCF (CASSCF) and the valence‐CI CASSCF were employed. The subsequent MRSDCI calculations were continued until the reference space included all configuration state functions (CSFs) of the MCSCF wave function with a coefficient larger than 0.01 [MRSDCI(0.01)]. The higher level basis sets in this study were all based on van Duijneveldt’s C(13s 8p) and H(6s) and extensions of that basis set. The study shows in a consistent way that both the one‐ and n‐particle spaces are saturated at the highest level of theory. The study has revealed that in addition to the well known increase of the quadrupole moment due to the inclusion of polarizing functions in the basis (typically 0.20 a.u.), the inclusion of electronic correlation in the model wave function as well as vibrational corrections will decrease the quadrupole moment significantly more, −0.66, −0.49, and −0.36 a.u., for the correlation correction and zero‐point correction for HCCH and DCCD, respectively. The most accurate computations predict the quadrupole moment of HCCH, including zero‐point correction, to be 4.29±0.12 a.u., which discriminates the experimental estimates of 4.03±0.30, 4.28±0.30, and 4.57±0.30 a.u. (the first being the favored value). The quadrupole moment of DCCD is computed to 4.42±0.10 a.u. In the study it was observed that in contradiction to previous experiences the use of the model equilibrium geometries rather than the experimental geometry gives a smoother convergence as the level of theory is increased. The effects of basis set quality and electron correlation on the quadrupole moment are studied in detail. These effects are analyzed with reference to the redistribution of the electronic charge.