Investigation of the Effect of Solvents on the Synthesis of Aza-flavanone from Aminochalcone Facilitated by Halogen Bonding.

It has been recognized that CBr4 can give rise to a noncovalent interaction known as halogen bond (XB). CBr4 was found to catalyze, in terms of XB formation, the transformation of 2'-aminochalcone to aza-flavanone through an intramolecular Michael addition reaction. The impact of XB and the resulting yield of aza-flavanone exhibited a pronounced dependence on the characteristics of the solvent. Notably, yields of 88% in ethanol and 33% in DMSO were achieved, while merely a trace amount of the product was detected in benzene. In this work, we use a computational modeling study to understand this variance in yield. The reaction is modeled at the level of density functional theory (based on the M06-2X exchange-correlation functional) with all-electron basis sets of triple-ζ quality. Grimme's dispersion correction is incorporated to account for the noncovalent interactions accurately. Harmonic frequency calculations are carried out to establish the character of the optimized structures (minimum or saddle point). Our calculations confirm the formation of an XB between CBr4 and the reacting species and its role in lowering the activation energy barrier. Stronger orbital interactions and significant lowering of the steric repulsion were found to be important in lowering the activation barrier. The negligible yield in the nonpolar solvent benzene may be attributed to the high activation energy as well as the inadequate stabilization of the zwitterionic intermediate. In ethanol, a protic solvent, additional H-bonding contributes to further lowering of the activation barrier and better stabilization of the zwitterionic intermediate. The combined effects of solvent polarity, XB, and H-bond are likely to give rise to an excellent yield of aza-flavanone in ethanol.

Semiclassical Dynamics on Machine-Learned Coupled Multireference Potential Energy Surfaces: Application to the Photodissociation of the Simplest Criegee Intermediate.

Determination of high-dimensional potential energy surfaces (PESs) and nonadiabatic couplings have always been quite challenging. To this end, machine learning (ML) models, trained with a finite set of ab initio data, allow accurate prediction of such properties. To express the PESs in terms of atomic contributions is the cornerstone of any ML based technique because it can be easily scaled to large systems. In this work, we have constructed high fidelity PESs and nonadiabatic coupling terms at the CASSCF level of ab initio data using a machine learning technique, namely, kernel-ridge regression. Additional MRCI-level calculations were carried out to assess the quality of the PESs. We use these machine-learned PESs and nonadiabatic couplings to simulate excited-state molecular dynamics based on Tully's fewest-switches surface hopping method (FSSH). FSSH is a semiclassical method in which nuclei move on the PESs due to the electrons according to the laws of classical mechanics. Nonadiabatic effects are taken into account in terms of transitions between PESs. We apply this scheme to study the O-O photodissociation of the simplest Criegee intermediate (CH2OO). The FSSH trajectories were initiated on the lowest optically bright singlet excited state (S2) and propagated along the three most important internal coordinates, namely, O-O and C-O bond distances and the COO bond angle. Some of the trajectories end up on energetically lower PESs as a result of radiationless transfer through conical intersections. All of the trajectories lead to the dissociation of the O-O bond due to the dissociative nature of the excited PESs through one of the two dissociative channels. The simulation reveals that there is about 88.4% probability of dissociation through the lower channel leading to the H2CO (X1A1) and O (1D) products, whereas there is only 11.6% probability of dissociation through the upper channel leading to H2CO (a3A″) and O (3P) products.

Recent Advances in the Study of Negative-Ion Resonances Using Multiconfigurational Propagator and a Complex Absorbing Potential.

The transient resonances are a challenge to bound state quantum mechanics. These states lie in the continuum part of the spectrum of the Hamiltonian. For this, one has to treat a continuum problem due to electron-molecule scattering and the many-electron correlation problem simultaneously. Moreover, the description of a resonance requires a wavefunction that bridges the part that resembles a bound state with another that resembles a continuum state such that the continuity of the wavefunction and its first derivative with respect to the distance between the incoming projectile and the target is maintained. A review of the recent advances in the theoretical investigation of the negative-ion resonances (NIR) is presented. The NIRs are ubiquitous in nature. They result from the scattering of electrons off of an atomic or molecular target. They are important for numerous chemical processes in upper atmosphere, space and even biological systems. A contextual background of the existing theoretical methods as well as the newly-developed multiconfigurational propagator tools based on a complex absorbing potential are discussed.

CBr4 catalyzed activation of α,ß-unsaturated ketones.

We have shown here that weak interactions such as halogen bonding (XB) can be used to activate the carbonyl group of α,ß-unsaturated ketones. Carbon tetrabromide (CBr4) has been used as the sole reagent for the selective synthesis of flavanones and aza-flavanones from the corresponding 2'-hydroxy- and 2'-aminochalcones under metal-free and additive-free conditions. DFT calculations support the catalytic role of XB between the oxygen of chalcones and CBr4 in these reactions.

Investigation of negative-ion resonances using a subspace-projected multiconfigurational electron propagator perturbed with a complex absorbing potential.

The transient negative-ion resonances found in scattering experiments are important intermediates in many chemical processes. These metastable states correspond to the continuum part of the Hamiltonian of the projectile-target composite system. Usual bound-state electronic structure methods are not applicable for these. In this work, we develop a subspace-projection method in connection with an electron propagator (EP) defined in terms of a complete-active-space self-consistent-field initial state. The target Hamiltonian (H) is perturbed by a complex absorbing potential (CAP) for the analytical continuation of the spectrum of H to complex eigenvalues associated with the continuum states. The resonance is identified as a pole of the EP, which is stable with respect to variations in the strength of the CAP. The projection into a small subspace reduces the size of the complex matrices to be diagonalized, minimizes the computational cost, and affords some insight into the orbitals that are likely to play some role in the capture of the projectile. Two molecular (Πg2N2 - and 2Π CO-) and an atomic shaperesonance (2P Be-) are investigated using this method. The position and width of the resonances are in good agreement with the previously reported values.

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 H perturbed by a complex absorbing potential (CAP) and a multiconfigurational self-consistent field (MCSCF) initial state to study these resonances. Perturbation of H 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 H 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.

A dinuclear [{(p-cym)Ru(II)Cl}2(µ-bpytz˙(-))](+) complex bridged by a radical anion: synthesis, spectroelectrochemical, EPR and theoretical investigation (bpytz = 3,6-bis(3,5-dimethylpyrazolyl)1,2,4,5-tetrazine; p-cym = p-cymene).

The reaction of the chloro-bridged dimeric precursor [{(p-cym)Ru(II)Cl}(µ-Cl)]2 (p-cym = p-cymene) with the bridging ligand 3,6-bis(3,5-dimethylpyrazolyl)-1,2,4,5-tetrazine (bpytz) in ethanol results in the formation of the dinuclear complex [{(p-cym)Ru(II)Cl}2(µ-bpytz˙(-))](+), [1](+). The bridging tetrazine ligand is reduced to the anion radical (bpytz˙(-)) which connects the two Ru(II) centres. Compound [1](PF6) has been characterised by an array of spectroscopic and electrochemical techniques. The radical anion character has been confirmed by magnetic moment (corresponding to one electron paramagnetism) measurement, EPR spectroscopic investigation (tetrazine radical anion based EPR spectrum) as well as density functional theory based calculations. Complex [1](+) displays two successive one electron oxidation processes at 0.66 and 1.56 V versus Ag/AgCl which can be attributed to [{(p-cym)Ru(II)C}2(µ-bpytz˙(-))](+)/[{(p-cym)Ru(II)Cl}2(µ-bpytz)](2+) and [{(p-cym)Ru(II)Cl}2(µ-bpytz)](+)/[{(p-cym)Ru(III)Cl}2(µ-bpytz)](2+) processes (couples I and II), respectively. The reduction processes (couple III-couple V), which are irreversible, likely involve the successive reduction of the bridging ligand and the metal centres together with loss of the coordinated chloride ligands. UV-Vis-NIR spectroelectrochemical investigation reveals typical tetrazine radical anion containing bands for [1](+) and a strong absorption in the visible region for the oxidized form [1](2+), which can be assigned to a Ru(II) → π* (tetrazine) MLCT transition. The assignment of spectroscopic bands was confirmed by theoretical calculations.

Quantum dynamical investigation of the simplest Criegee intermediate CH2OO and its O-O photodissociation channels.

The singlet electronic potential energy surfaces for the simplest Criegee intermediate CH2OO are computed over a two-dimensional reduced subspace of coordinates, and utilized to simulate the photo-initiated dynamics on the S2 (B) state leading to dissociation on multiple coupled excited electronic states. The adiabatic electronic potentials are evaluated using dynamically weighted state-averaged complete active space self-consistent field theory. Quasi-diabatic states are constructed from the adiabatic states by maximizing the charge separation between the states. The dissociation dynamics are then simulated on the diabatically coupled excited electronic states. The B ← X electronic transition with large oscillator strength was used to initiate dynamics on the S2 (B) excited singlet state. Diabatic coupling of the B state with other dissociative singlet states results in about 5% of the population evolving to the lowest spin-allowed asymptote, generating H2CO (X (1)A1) and O ((1)D) fragments. The remaining ∼95% of the population remains on repulsive B state and dissociates to H2CO (a (3)A″) and O ((3)P) products associated with a higher asymptotic limit. Due to the dissociative nature of the B state, the simulated electronic absorption spectrum is found to be broad and devoid of any vibrational structure.

Exploring Copper Oxide Cores Using the Projected Hartree-Fock Method.

Coupled binuclear copper oxide cores are present in the active sites of some of the very common metalloenzymes found in most living organisms. The correct theoretical description of the interconversion between the two dominant structural isomers of this core, namely, side-on µ-η(2):η(2)-peroxodicopper(II) and bis(µ-oxo)-dicopper(III), is challenging since it requires a method that can provide a balanced description of static and dynamic correlations. We investigate this problem using our recently developed projected Hartree-Fock method (PHF). Here, the spin and complex conjugation symmetries of the trial wave function are deliberately broken and restored in a variation-after-projection scheme. The projected wave function carries good quantum numbers, has multireference character, and accounts for static and some dynamic correlation. Most importantly, the calculations are done at a mean-field computational cost allowing us to address large systems at a modest expense. The interconversion is studied here for the bare [Cu2O2](2+) core using a variety of projection methods (SUHF, SGHF, KSUHF, KSGHF). The results seem to be on par with much more demanding traditional multireference methods.

Projected quasiparticle theory for molecular electronic structure.

We derive and implement symmetry-projected Hartree-Fock-Bogoliubov (HFB) equations and apply them to the molecular electronic structure problem. All symmetries (particle number, spin, spatial, and complex conjugation) are deliberately broken and restored in a self-consistent variation-after-projection approach. We show that the resulting method yields a comprehensive black-box treatment of static correlations with effective one-electron (mean-field) computational cost. The ensuing wave function is of multireference character and permeates the entire Hilbert space of the problem. The energy expression is different from regular HFB theory but remains a functional of an independent quasiparticle density matrix. All reduced density matrices are expressible as an integration of transition density matrices over a gauge grid. We present several proof-of-principle examples demonstrating the compelling power of projected quasiparticle theory for quantum chemistry.

Investigation of 2P Be- shape resonances using a quadratically convergent complex multiconfigurational self-consistent field method.

We develop, implement, and apply a quadratically convergent complex multiconfigurational self-consistent field method (CMCSCF) that uses the complex scaling theorem of Aguilar, Balslev, and Combes within the framework of the multiconfigurational self-consistent field method (MCSCF) in order to theoretically investigate the resonances originated due to scattering of a low-energy electron off of a neutral or an ionic target (atomic or molecular). The need to scale the electronic coordinates of the Hamiltonian as prescribed in the complex scaling theorem requires the use of a modified second quantization algebra suitable for biorthonormal spin orbital bases. In order to control the convergence to a stationary point in the complex energy hypersurface, a modified step-length control algorithm is incorporated. The position and width of 2P Be- shape resonances are calculated by inspecting the continuum states of Be-. To our knowledge, this is the first time that CMCSCF has been directly used to determine electron-atom/molecule scattering resonances. We demonstrate that both relaxation and nondynamical correlation are important for accurately describing shape resonances. For all of the calculations, the quadratically convergent CMCSCF was found to converge to the correct stationary point with a tolerance of 1.0 x 10(-10) au for the energy gradient within 10 iterations or less.