Complete Active Space Self-consistent Field Calculations Research Articles

Orbitals, Occupation Numbers, and Band Structure of Short One-Dimensional Cadmium Telluride Polymers.

Recent work found that soldering CdTe quantum dots together with a molecular CdTe polymer yielded field-effect transistors with much greater electron mobility than quantum dots alone. We present a computational study of the CdTe polymer using the active-space variational two-electron reduced density matrix (2-RDM) method. While analogous complete active-space self-consistent field (CASSCF) methods scale exponentially with the number of active orbitals, the active-space variational 2-RDM method exhibits polynomial scaling. A CASSCF calculation using the (48o,64e) active space studied in this paper requires 1024 determinants and is therefore intractable, while the variational 2-RDM method in the same active space requires only 2.1 × 107 variables. Natural orbitals, natural-orbital occupations, charge gaps, and Mulliken charges are reported as a function of polymer length. The polymer, we find, is strongly correlated, despite possessing a simple sp3-hybridized bonding scheme. Calculations reveal the formation of a nearly saturated valence band as the polymer grows and a charge gap that decreases sharply with polymer length.

MagneticAnisotropyandField-inducedSlow RelaxationofMagnetizationinTetracoordinate CoII Compound[Co(CH₃-im)₂Cl₂

Static and dynamic magnetic properties of the tetracoordinate CoII complex [Co(CH3-im)2Cl2], (1, CH3-im = N-methyl-imidazole), studied using thorough analyses of magnetometry, and High-Frequency and -Field EPR (HFEPR) measurements, are reported. The study was supported by ab initio complete active space self-consistent field (CASSCF) calculations. It has been revealed that 1 possesses a large magnetic anisotropy with a large rhombicity (magnetometry: D = −13.5 cm−1, E/D = 0.33; HFEPR: D = −14.5(1) cm−1, E/D = 0.16(1)). These experimental results agree well with the theoretical calculations (D = −11.2 cm−1, E/D = 0.18). Furthermore, it has been revealed that 1 behaves as a field-induced single-ion magnet with a relatively large spin-reversal barrier (Ueff = 33.5 K). The influence of the Cl–Co–Cl angle on magnetic anisotropy parameters was evaluated using the CASSCF calculations.

Ab Initio Crystal Field for Lanthanides.

An ab initio methodology for the first-principle derivation of crystal-field (CF) parameters for lanthanides is described. The methodology is applied to the analysis of CF parameters in [Tb(Pc)2 ]- (Pc=phthalocyanine) and Dy4 K2 ([Dy4 K2 O(OtBu)12 ]) complexes, and compared with often used approximate and model descriptions. It is found that the application of geometry symmetrization, and the use of electrostatic point-charge and phenomenological CF models, lead to unacceptably large deviations from predictions based on ab initio calculations for experimental geometry. It is shown how the predictions of standard CASSCF (Complete Active Space Self-Consistent Field) calculations (with 4f orbitals in the active space) can be systematically improved by including effects of dynamical electronic correlation (CASPT2 step) and by admixing electronic configurations of the 5d shell. This is exemplified for the well-studied Er-trensal complex (H3 trensal=2,2',2"-tris(salicylideneimido)trimethylamine). The electrostatic contributions to CF parameters in this complex, calculated with true charge distributions in the ligands, yield less than half of the total CF splitting, thus pointing to the dominant role of covalent effects. This analysis allows the conclusion that ab initio crystal field is an essential tool for the decent description of lanthanides.

Improved virtual orbitals in state specific multireference perturbation theory for prototypes of quasidegenerate electronic structure.

The state-specific multireference perturbation theory (SSMRPT) with an improved virtual orbital complete active space configuration interaction (IVO-CASCI) reference function [called as IVO-SSMRPT] is used to investigate the energy surface, geometrical parameters, molecular properties of spectroscopic interest for the systems/situations [such as BeH2, BeCH2, MgCH2, Si2H4, unimolecular dissociation of H2CO, and intramolecular reaction pathways of 1,3-butadiene] where the effect of quasidegeneracy cannot be neglected. The merit of using the IVO-CASCI rather than complete active space self-consistent field (CASSCF) is that it is free from iterations beyond those in the initial SCF calculation and the convergence difficulties that plague CASSCF calculations with increasing size of the CAS. While IVO-CASCI describes the non-dynamical correlation, the SSMRPT scheme is a good second-order perturbative approximation to account for the rest of the correlation energy. Our IVO-SSMRPT method is instrumental in avoiding intruder states in an size-extensive manner and allows the revision of the content of wave function in the model space. It can treat model as well as real systems with predictive accuracy, as is evident from the fairly nice accordance between our estimates, and high-level theoretical results. Our estimates also corroborate well with some experimental findings.

Combining the Complete Active Space Self-Consistent Field Method and the Full Configuration Interaction Quantum Monte Carlo within a Super-CI Framework, with Application to Challenging Metal-Porphyrins.

A novel stochastic Complete Active Space Self-Consistent Field (CASSCF) method has been developed and implemented in the Molcas software package. A two-step procedure is used, in which the CAS configuration interaction secular equations are solved stochastically with the Full Configuration Interaction Quantum Monte Carlo (FCIQMC) approach, while orbital rotations are performed using an approximated form of the Super-CI method. This new method does not suffer from the strong combinatorial limitations of standard MCSCF implementations using direct schemes and can handle active spaces well in excess of those accessible to traditional CASSCF approaches. The density matrix formulation of the Super-CI method makes this step independent of the size of the CI expansion, depending exclusively on one- and two-body density matrices with indices restricted to the relatively small number of active orbitals. No sigma vectors need to be stored in memory for the FCIQMC eigensolver--a substantial gain in comparison to implementations using the Davidson method, which require three or more vectors of the size of the CI expansion. Further, no orbital Hessian is computed, circumventing limitations on basis set expansions. Like the parent FCIQMC method, the present technique is scalable on massively parallel architectures. We present in this report the method and its application to the free-base porphyrin, Mg(II) porphyrin, and Fe(II) porphyrin. In the present study, active spaces up to 32 electrons and 29 orbitals in orbital expansions containing up to 916 contracted functions are treated with modest computational resources. Results are quite promising even without accounting for the correlation outside the active space. The systems here presented clearly demonstrate that large CASSCF calculations are possible via FCIQMC-CASSCF without limitations on basis set size.

Theoretical investigations of absorption and fluorescence spectra of protonated pyrene.

The equilibrium geometry and 75 vibrational normal-mode frequencies of the ground and first excited states of protonated pyrene isomers were calculated and characterized in the adiabatic representation by using the complete active space self-consistent field (CASSCF) method. Electronic absorption spectra of solid neon matrixes in the wavelength range 495-415 nm were determined by Maier et al. and they were analyzed using time-dependent density functional theory calculations (TDDFT). CASSCF calculations and absorption and emission spectra simulations by one-photon excitation equations were used to optimize the excited and ground state structures of protonated pyrene isomers. The absorption band was attributed to the S0 → S1 electronic transition in 1H-Py(+), and a band origin was used at 20580.96 cm(-1). The displaced harmonic oscillator approximation and Franck-Condon approximation were used to simulate the absorption spectrum of the (1) (1)A' ← X[combining tilde](1)A' transition of 1H-Py(+), and the main vibronic transitions were assigned for the first ππ* state. It shows that the vibronic structures were dominated by one of the eight active totally symmetric modes, with ν15 being the most crucial. This indicates that the electronic transition of the S1((1)A') state calculated in the adiabatic representation effectively includes a contribution from the adiabatic vibronic coupling through Franck-Condon factors perturbed by harmonic oscillators. The present method can adequately reproduce experimental absorption and fluorescence spectra of a gas phase.

Enhanced computational efficiency in the direct determination of the two-electron reduced density matrix from the anti-Hermitian contracted Schrödinger equation with application to ground and excited states of conjugated π-systems.

Determination of the two-electron reduced density matrix (2-RDM) from the solution of the anti-Hermitian contracted Schrödinger equation (ACSE) yields accurate energies and properties for both ground and excited states. Here, we develop a more efficient method to solving the ACSE that uses second-order information to select a more optimal step towards the solution. Calculations on the ground and excited states of water, hydrogen fluoride, and conjugated π systems show that the improved ACSE algorithm is 10-20 times faster than the previous ACSE algorithm. The ACSE can treat both single- and multi-reference electron correlation with the initial 2-RDM from a complete-active-space self-consistent-field (CASSCF) calculation. Using the improved algorithm, we explore the relationship between truncation of the active space in the CASSCF calculation and the accuracy of the energy and 2-RDM from the ACSE calculation. The accuracy of the ACSE, we find, is less sensitive to the size of the active space than the accuracy of other wavefunction methods, which is useful when large active space calculations are computationally infeasible.

Fully relativistic complete active space self-consistent field for large molecules: quasi-second-order minimax optimization.

We develop an efficient algorithm for four-component complete active space self-consistent field (CASSCF) methods on the basis of the Dirac equation that takes into account spin-orbit and other relativistic effects self-consistently. Orbitals are optimized using a trust-region quasi-Newton method with Hessian updates so that energies are minimized with respect to rotations among electronic orbitals and maximized with respect to rotations between electronic and positronic orbitals. Utilizing density fitting and parallel computation, we demonstrate that Dirac-Coulomb CASSCF calculations can be routinely performed on systems with 100 atoms and a few heavy-elements. The convergence behavior and wall times for octachloridodirhenate(III) and a tungsten methylidene complex are presented. In addition, the excitation energies of octachloridodirhenate(III) are reported using a state-averaged variant.

Excited state proton transfer dynamics of thioacetamide in S2(ππ*) state: resonance Raman spectroscopic and quantum mechanical calculations study.

The photophysics and photochemistry of thioacetamide (CH3CSNH2) after excitation to the S2 electronic state were investigated by using resonance Raman spectroscopy in conjunction with the complete active space self-consistent field (CASSCF) method and density functional theory (DFT) calculations. The A-band resonance Raman spectra in acetonitrile, methanol, and water were obtained at 299.1, 282.4, 266.0, 252.7, and 245.9 nm excitation wavelengths to probe the structural dynamics of thioacetamide in the S2 state. CASSCF calculations were done to determine the transition energies and structures of the lower-lying excited states, the conical intersection points CI(S2/S1) and CI(S1/S0), and intersystem crossing points. The structural dynamics of thioacetamide in the S2 state was revealed to be along eight Franck-Condon active vibrational modes ν15, ν11, ν14, ν10, ν8, ν12, ν18, and ν19, mostly in the CC/CS/CN stretches and the CNH8,9/CCH5,6,7/CCN/CCS in-plane bends as indicated by the corresponding normal mode descriptions. The S2 → S1 decay process via the S2/S1 conical intersection point as the major channel were excluded. The thione-thiol photoisomerization reaction mechanism of thioacetamide via the S2,FC → S'1,min excited state proton transfer (ESPT) reaction channel was proposed.

Decay dynamics of α,β-carboxylic methyl esters (CH3OCOCH:CHR) in the lower-lying excited states--resonance Raman and complete active space self-consistent field calculation study.

The photophysics of two α,β-carboxylic methyl esters after excitation to the light absorbing S2(ππ(*)) state were studied by using the resonance Raman spectroscopy and complete active space self-consistent field (CASSCF) method calculations. The vibrational spectra were assigned on the basis of the experimental measurements and the B3LYP/6-31G(d) computations, as well as the normal mode analysis. The A-band resonance Raman spectra of methyl 2,4-pentadienoate (M24PDA) and methyl trans cronoate (MTCA) were measured to probe the structural dynamics in Franck-Condon region. CASSCF calculations were done to obtain the minimal excitation energies and geometric structures of the lower-lying singlet and triplet excited states, and the curve-crossing points. It was revealed that the short-time structural dynamics of M24PDA was dominated by the Cα=Cβ-C4=C5 stretch coordinate, while that of MTCA was mostly along the Cα=Cβ and the C=O stretch motion. Comparison of the structural dynamics of M24PDA and MTCA with that of 3-methyl-3-pentene-2-one (3M3P2O) indicated that the structural dynamics of MTCA is similar to that of 3M3P2O but different than that of M24PDA in that the variation of the Raman intensity ratios for ν7/ν8, (ν7+ν8)/2ν8, (ν7+2ν8)/3ν8, (ν7+3ν8)/4ν8 of MTCA is similar to that of 3M3P2O but different from that of M24PDA. It is found that the substitution of methyl group in the α(')-position of α,β-enones by methoxyl group does not substantially affect the short-time structural dynamics, while the substitution of vinyl group in the β-position changes significantly the short-time structural dynamics and the subsequent decay processes. A detailed decay mechanism is proposed. Two sub-processes which consider the reconjugation and the subsequent charge-transfer reaction of O=C-Cα=Cβ chromophore were postulated to describe the variation of short-time structural dynamics with the different substitution.

Density functional theory versus complete active space self-consistent field investigation of the half-metallic character of graphite-like and amorphous carbon nanoparticles.

Model carbon nanoparticles representative of the graphite-like and amorphous domains of active carbon are investigated with density functional theory (DFT) and complete active space self-consistent field (CASSCF) methods. Cyclic carbon clusters containing conjugated carbene groups are found to undergo Jahn-Teller distortion. More importantly, the half-metallicity, that is, the equal or similar stability of various spin states, previously suggested by DFT calculations for both types of nanosized clusters is confirmed by CASSCF calculations. Furthermore, the model carbon clusters are found to possess a multiconfigurational electronic structure dominated by high-spin configurations. When compared to CASSCF results, the single-reference DFT predicts proper electronic structures, characterized by antiferromagnetically coupled electron pairs, at the expense of spin contamination as a reflection of the multiconfigurational character. In fact, spin contamination, which is normally viewed as an error, does not corrupt the energetics of the half-metallic systems and therefore does not preclude the applicability of DFT to such systems.

Two C3 -symmetric Dy3III complexes with triple di-μ-methoxo-μ-phenoxo bridges, magnetic ground state, and single-molecule magnetic behavior.

Two series of isostructural C(3)-symmetric Ln(3) complexes Ln(3)⋅[BPh(4)] and Ln(3)⋅0.33[Ln(NO(3))(6)] (in which Ln(III) =Gd and Dy) have been prepared from an amino-bis(phenol) ligand. X-ray studies reveal that Ln(III) ions are connected by one μ(2)-phenoxo and two μ(3)-methoxo bridges, thus leading to a hexagonal bipyramidal Ln(3)O(5) bridging core in which Ln(III) ions exhibit a biaugmented trigonal-prismatic geometry. Magnetic susceptibility studies and ab initio complete active space self-consistent field (CASSCF) calculations indicate that the magnetic coupling between the Dy(III) ions, which possess a high axial anisotropy in the ground state, is very weakly antiferromagnetic and mainly dipolar in nature. To reduce the electronic repulsion from the coordinating oxygen atom with the shortest Dy-O distance, the local magnetic moments are oriented almost perpendicular to the Dy(3) plane, thus leading to a paramagnetic ground state. CASSCF plus restricted active space state interaction (RASSI) calculations also show that the ground and first excited state of the Dy(III) ions are separated by approximately 150 and 177 cm(-1), for Dy(3)⋅[BPh(4)] and Dy(3)⋅0.33[Dy(NO(3))(6)], respectively. As expected for these large energy gaps, Dy(3)⋅[BPh(4)] and Dy(3)⋅0.33[Dy(NO(3)(6)] exhibit, under zero direct-current (dc) field, thermally activated slow relaxation of the magnetization, which overlap with a quantum tunneling relaxation process. Under an applied Hdc field of 1000 Oe, Dy(3)⋅[BPh(4)] exhibits two thermally activated processes with U(eff) values of 34.7 and 19.5 cm(-1), whereas Dy(3)⋅0.33[Dy(NO(3))(6)] shows only one activated process with Ueff =19.5 cm(-1).

Decay Dynamics of 3‐methyl‐3‐pentene‐2‐one from the light absorbing S2(ππ*) state ‐ Resonance Raman Spectroscopy and CASSCF Study

The photophysics of 3‐methyl‐3‐pentene‐2‐one (3M3P2O) after excitation to the S2(ππ*) electronic state were studied using the resonance Raman spectroscopy and complete active space self‐consistent field (CASSCF) method calculations. The A‐band resonance Raman spectra were obtained in cyclohexane, acetonitrile, and methanol with excitation wavelengths in resonance with the first intense absorption band to probe the structural dynamics of 3M3P2O. The B3LYP‐TD/6‐31++G(d, p) computation was carried out to determine the relative A‐band resonance Raman intensities of the fundamental modes, and the result was used to reproduce the corresponding fundamental band intensities of the 223.1 nm resonance Raman spectrum and thus to examine whether the vibronic‐coupling existed in Franck‐Condon region or not. CASSCF calculations were carried out to determine the minimal singlet excitation energies of S1, FC, S1,min (nπ*), S2, FC, S2,min (ππ*), the transition energies of the conical intersection points Sn/Sπ, Sn/S0, and the optimized excited state geometries as well as the geometry structures of the conical intersection points. The A‐band short‐time structural dynamics and the corresponding decay dynamics of 3M3P2O were obtained by the analysis of the resonance Raman intensity pattern and CASSCF computations. It was revealed that the initial structural dynamics of 3M3P2O was towards the simultaneous C3=C4 and C2=O7 bond elongation, with the C3=C4 bond length lengthening greater at the very beginning, whereas the C2=O7 bond length changing greater at the later evolution time before reaching the CI(S2/S1) conical intersection point. The decay dynamics from S2(ππ*) to S1(nπ*) via S2(ππ*)/S1(nπ*) in singlet realm and from S1(nπ*) to T1(nπ*) via ISC[S1(nπ*)/T2(ππ*)/T1(nπ*)] in triplet realm are proposed. Copyright © 2014 John Wiley & Sons, Ltd.

On the use of reduced active space in CASSCF calculations

The complete active space self-consistent field (CASSCF) method is one of the most used approaches to explore theoretically non-adiabatic photochemical processes in medium-size molecular systems. It is also frequently utilized in direct dynamics studies because this method offers a reliable description of the electronic state mixing in the regions of surface crossings (conical intersections). In this context, however, the large computational demand required to perform such on-the-fly molecular dynamics simulations using CASSCF as the electronic structure method means that only relatively small active space can be handled (typically not more than 10 electrons distributed in 10 orbitals). In this article, we present some guidelines to reduce the active space size in CASSCF calculations in order to decrease the computational cost necessary to perform, for example, molecular dynamics simulations. Three important criteria are considered: (i) the degradation of the accuracy in the description of the potential energy surface following the reduction of the active space, (ii) the stability of the reduced active space across the global potential energy surface, and (iii) the cost of the CASSCF calculation using the reduced active space. Two illustrations are given. The first one is the benzene to benzvalene S1 photochemical pathway, the second one is the photoisomerization of thiomethyl para-coumaric acid, the chromophore in photoactive yellow protein.

N1s and O1s double ionization of the NO and N2O molecules.

Single-site N1s and O1s double core ionisation of the NO and N2O molecules has been studied using a magnetic bottle many-electron coincidence time-of-flight spectrometer at photon energies of 1100 eV and 1300 eV. The double core hole energies obtained for NO are 904.8 eV (N1s(-2)) and 1179.4 eV (O1s(-2)). The corresponding energies obtained for N2O are 896.9 eV (terminal N1s(-2)), 906.5 eV (central N1s(-2)), and 1174.1 eV (O1s(-2)). The ratio between the double and single ionisation energies are in all cases close or equal to 2.20. Large chemical shifts are observed in some cases which suggest that reorganisation of the electrons upon the double ionization is significant. Δ-self-consistent field and complete active space self-consistent field (CASSCF) calculations were performed for both molecules and they are in good agreement with these results. Auger spectra of N2O, associated with the decay of the terminal and central N1s(-2) as well as with the O1s(-2) dicationic states, were extracted showing the two electrons emitted as a result of filling the double core holes. The spectra, which are interpreted using CASSCF and complete active space configuration interaction calculations, show atomic-like character. The cross section ratio between double and single core hole creation was estimated as 1.6 × 10(-3) for nitrogen at 1100 eV and as 1.3 × 10(-3) for oxygen at 1300 eV.

Theoretical investigation of two model systems for molecular photoswitch functionality. I. 2-(4-nitropyrimidin-2-yl)ethenol

The ground and five lowest-lying electronically excited singlet states of 2-(4-nitropyrimidin-2-yl)ethenol (NPE) have been studied theoretically using the complete active space self-consistent-field (CASSCF), Møller-Plesset second-order perturbation theory (MP2) and second-order multi-configurational perturbation theory (CASPT2) methods. The molecule can be regarded as being composed of a frame and a crane component and is characterised by the existence of two planar minima of similar energy on the ground-state potential energy (PE) surface. This work explores the possibility of an excited-state intramolecular hydrogen transfer (ESIHT) process in NPE. A hypothetical reaction coordinate has been constructed for NPE. State-averaged CASSCF and CASPT2 calculations of the six lowest-lying singlet states have been performed for the isomerisation. Adiabatic and simplified quasi-diabatic PE and transition dipole moment functions have been constructed. The computations indicate that there exist substantial barriers for the rotation process on the adiabatic PE surfaces of all the five excited states investigated. The six quasi-diabatic electronic states considered here decompose into two classes based on whether the electronic wave functions depend weakly or strongly on the nuclear displacement, subject to the effect of the torsion on relevant molecular orbitals.

Effect of Initial Orientation on the Laser-Induced Cycloaddition Reaction of Benzene and Ethylene

The [2 + 2] photocycloaddition reaction of benzene and ethylene was investigated by semiclassical dynamics simulation and complete active space self-consistent field (CASSCF)ab initiocalculations. Following laser excitation of the benzene molecule, two mechanisms were observed depending on the location of the second C of ethylene in relation to the hexagonal prism space defined by the first C and the plane of the benzene ring. Synchronous formation of two bonds was observed when the second C is outside the prism space; an asynchronous mechanism is observed otherwise. Charge transfer was observed only in the asynchronous mechanism; CASSCF calculations suggest that the asynchronous mechanism involves a barrierless path from the Frank-Condon point to a conical intersection, while the synchronous mechanism involves 0.8 eV barrier. These results are consistent with a higher quantum yield observed in the simulations for the asynchronous pathway.

Excited State Structural Dynamics of <em>A</em>-Band of 4-Nitroimidazole

The A-band structural dynamics of 4-nitroimidazole (4NI) were studied using resonance Raman spectroscopy and quantum mechanical calculations, and the vibrational spectra, UV absorption spectra, fluorescence spectra, and A-band resonance Raman spectra were assigned. The resonance Raman spectra of 4-nitroimidazole were obtained in methanol with excitation wavelengths in resonance with the first intense absorption band, to probe the short-time structural dynamics. The optimized geometric structures and the excitation energies of the singlet excited states S1(nOπ*) and S2(ππ*), and the conical intersection point S1(nOπ*)/ S2(ππ*), were computed at the complete active space self-consistent field (CASSCF)/6-31G(d) theory level. The intensity patterns of the A-band resonance Raman spectra were analyzed, and the results, together with those of the CASSCF calculations, revealed that the major decay channel initiated from the S2(ππ*) state was S2, FC→S2, min(ππ*)→S0 radiation.

Diabatic Molecular Orbitals, Potential Energies, and Potential Energy Surface Couplings by the 4-fold Way for Photodissociation of Phenol.

Complete-active-space self-consistent-field (CASSCF) calculations provide useful reference wave functions for configuration interaction or perturbation theory calculations of excited-state potential energy surfaces including dynamical electron correlation. However, the canonical molecular orbitals (MOs) of CASSCF calculations usually have mixed character in regions of strong interaction of two or more electronic states; therefore, they are unsuitable for diabatization using the configurational uniformity approach. Here, CASSCF diabatic MOs for phenol have been obtained by the 4-fold way, and comparison to the CASSCF canonical MOs shows that they are much smoother. Using these smooth CASSCF diabatic MOs, we performed direct diabatization calculations for the three low-lying states ((1)ππ, (1)ππ*, and (1)πσ*) and their diabatic (scalar) couplings at the dynamically correlated multiconfiguration quasidegenerate perturbation theory (MC-QDPT) level. We present calculations along the O-H stretching and C-C-O-H torsion coordinates for the nonadiabatic photodissociation of phenol to the phenoxyl radical and hydrogen atom. The seams of (1)ππ*/(1)πσ* and (1)ππ/(1)πσ* diabatic crossings are plotted as functions of these coordinates. We also present diabatization calculations for displacements along the out-of-plane ring distortion modes 16a and 16b of the phenyl group. The dominant coupling modes of the two conical intersections ((1)ππ*/(1)πσ* and (1)ππ/(1)πσ*) are discussed. The present diabatization method is confirmed to be valid even for significantly distorted ring structures by diabatization calculations along a reaction path connecting the planar equilibrium geometry of phenol to its strongly distorted prefulvenic form. The present work provides insight into the mode specificity of phenol photodissociation and shows that diabatization at the MC-QDPT level employing CASSCF diabatic MOs can be a good starting point for multidimensional dynamics calculations of photochemical reactions.

Electronic Structure of Cofactor−Substrate Reactant Complex Involved in the Methyl Transfer Reaction Catalyzed by Cobalamin-Dependent Methionine Synthase

Complete active space self-consistent field (CASSCF) computations followed by the second-order perturbation theory have been applied to investigate the electronic properties of a structural mimic of the reactant complex formed in the catalytic cycle of cobalamin-dependent methionine synthase (MetH). Two different structural models have been employed to analyze the reaction complex between methylcobalamin (MeCbl) and homocysteine (Hcy). The first model, referred to as the small model (SM), is based on a truncated corrin ring with inner conjugated macrocycle only and has symmetry constrain with respect to methylthiolate. The second is based on a full corrin ring, i.e., [Co(III)(corrin)]-Me(+)···(-)S-CH(3), without the side chains (which were replaced by hydrogen atoms) and referred to as the large model (LM). The active space chosen for both models includes all essential orbitals participating in the methyl transfer reaction. Although the CASSCF calculations are much more demanding for the LM (due to the structural complexity) than the SM, the results are fully consistent. The energetic of ionic and diradical states have been examined as a function of the C···S distance between the methyl group of MeCbl and the sulfur of the thiolate substrate for both models. The most important finding of the present work is the energetic variation of ionic and diradical states as a function of C···S distance. The two states cross each other at a C···S distance of 4.0 Å, i.e., for a distance shorter than ∼4.0 Å, the ionic state is energetically the lowest electronic state, while the diradical state becomes the lowest state at longer distances. However, the potential energy surface of the ionic state shows greater sensitivity with respect to the C···S distance than that of the diradical one. The former can be associated with S(N)2-type displacement, where the cleavage of the Co-C bond would be heterolytic, while the latter can be associated with an electron transfer (ET), where the cleavage is homolytic. Finally, the importance of this finding is briefly discussed in the context of MeCbl-dependent enzymatic catalysis.