Journal of Theoretical and Computational Chemistry

Titanium dioxide (TiO₂) nanoparticles are widely used in contaminant remediation, photocatalysis and solar cell manufacturing. The low-cost production of TiO₂ nanoparticles via the combustion of titanium tetrachloride (TiCl₄) in oxygen is thus an important industrial process. To accurately model the flame synthesis of TiO₂ nanoparticles, reliable thermodynamic data of Ti–O–Cl species are indispensable but often unavailable. We therefore carried out benchmark calculations, using the left-eigenstate completely renormalized singles, doubles and perturbative triples (CR-CC(2,3), aka CR-CCL) method with the cc-pVTZ basis set, to obtain the equilibrium structures and vibrational frequencies of selected Ti–O–Cl species; we then performed single-point CCSD(T)/aug-cc-pVLZ ($L=\mathrm{3–5}$) calculations to extrapolate the CCSD(T)/CBS energies. After analyzing the experimental and calculated enthalpy of selected Ti–O–Cl species, the standard enthalpy of formation of the TiOCl₂ molecule is determined to be $-$600.5kJ/mol at 298K. The standard enthalpy of all other Ti–O–Cl species are determined accordingly. Finally, we assessed the accuracy of 42 popular density functionals for the Ti–O–Cl species. Among these assessed functionals, the B98 functional, tightly followed by B97-1 and B3LYP, exhibits the best overall performance in the prediction of the thermochemistry of the Ti–O–Cl species.

Aspalathin and nothofagin are the major dihydrochalcones found in rooibos (Aspalathus linearis), which display anti-diabetic activities, but the mechanism is still unclear. In this paper, hSGLT2 (human sodium dependent glucose co-transporter 2), a target for diabetes mellitus, was built using homology modeling method. Molecular docking and dynamics simulations were carried out on aspalathin, nothofagin and SGLT2 complexes with dapagliflozin as positive control. The results show that both the binding energies and binding modes of aspalathin and nothofagin are similar to dapagliflozin, indicating that either component of rooibos may exhibit anti-diabetic effects through inhibiting SGLT2 receptor. However, the predicted permeability value of aspalathin and nothofagin is low, which may cause poor absorption, resulting in weak SGLT2 inhibition. Calculation results elucidate the possible inhibiting mechanism of aspalathin and nothofagin against SGLT2, and therefore enhance our understanding of anti-diabetic activities of rooibos.

A theoretical study on the selectivity of a series of [M(12C4)]${}^{+}$ (M = Li${}^{+}$, Na${}^{+}$, K${}^{+}$, 12C4 = 12-crown-4) complexes for F${}^{-}$, Cl${}^{-}$ and Br${}^{-}$ anions and a number of neutral molecules (CH₃CN, CH₃OH, NH₃, H₂O, py, and 12C4) is reported. At first, it was shown that in the gas phase among all studied halide anions and neutral molecules, halides have much more bonding interaction with all [M(12C4)]${}^{+}$ cations. Calculated interaction energies of above anions and [M(12C4)]${}^{+}$ cations decrease from F${}^{-}$ to Br${}^{-}$. Also the interaction energy of halide anions with [M(12C4)]${}^{+}$ complexes, decreases from [Li(12C4)]${}^{+}$ to [K(12C4)]${}^{+}$. The electron decomposition analysis showed that the bond between [M(12C4)]${}^{+}$ complexes and both the neutral and anion guests is mainly electrostatic in nature. Then the selectivity of [M(12C4)]${}^{+}$ complexes for studied anions and neutral molecules are compared in methanol, acetone, acetonitrile, and nitromethane solutions. It was shown that both the desolvation process of reactants and the strength of host–guest interactions have significant effect on the selectivities. Thus the selectivity of [Li(12C4)]${}^{+}$ cation for NH₃ and H₂O neutral molecules in solution, in contrast to the gas phase, is higher than that for bromide anion. The results of calculations showed that all [M(12C4)]${}^{+}$ complexes, specially [Li(12C4)]${}^{+}$, have high selectivity for F${}^{-}$ over other halide anions and neutral molecules.

Many proteins contain cofactors, such as heme, ATP and metal ions. Binding of cofactors is not only essential for their biological functions, but also can reshape the intrinsic energy landscape of protein molecules and modulate the folding and stability. However, the molecular mechanism of cofactor coupled protein folding is not well understood. In this work, we study the cofactor coupled folding of myoglobin, which is a typical cofactor (heme) containing protein, by performing molecular dynamics simulations with a structure-based protein model developed based on the energy landscape theory. We showed that the heme binding increases the stability of the myoglobin. More importantly, the heme binding tends to increase the protein folding cooperativity, and switch the folding process from a “three-state” mechanism to a “two-state” mechanism. We also showed that the folding pathways of the myoglobin can be modulated by the heme binding. By performing comparative simulations, we revealed that the above effects of heme binding are resulted from the heme induced folding of F-helix, which is otherwise unstructured at apo state, and the heme mediated contacting interactions around the heme binding site. The simulation results are consistent with available experimental data, and provide insights into the molecular mechanism of the effects of cofactor binding on the protein folding and stability.

Twisted conformations of ethylene molecule have diradical character and the second hyperpolarizability of these conformations is best described by the multiconfigurational self consistence field theory (MCSCF) wave function. Present calculation indicates that unrestricted density functional theory (UDFT) predicts second hyperpolarizability which is qualitatively correct for the intermediate diradical region. However, for the two extremities, i.e. rear diradical region and near diradical region, the second hyperpolarizability obtained by UDFT methods differ significantly from the MRCISD result. The BHHLYP and LC-BLYP ($\mu =0.47$) results of ${\gamma }_{\mathrm{\text{xxxx}}}$ are found to be in good agreement with the MRCISD result. Using the spin-projected UDFT methods almost similar results are obtained. The reasonably fair agreement between the calculated results of second hyperpolarizability obtained at the MRCISD and CASSCF(4,4) levels demonstrates that static electron correlation is the dominant feature of twisted ethylene.

Dichlorobis(L-proline) zinc(II) (DCBLPZ) is an excellent nonlinear optical (NLO) material because of its ability to exhibit high second harmonic generation and having significant optical transparency. In this work, electro-optical properties of the titled material has been thoroughly investigated by Hartree–Fock (HF) and Density functional theory using different basis sets in C1 symmetry. The calculated geometrical parametres and vibrational frequencies were found to be in good agreement with reported experimental results. Highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) studies were carried out to understand the intramolecular charge transfer within the molecule. Total dipole moment (${\mu }_{\mathrm{\text{tot}}}$), polarizability (${\alpha }_{\mathrm{\text{tot}}}$), anisotropy of polarizability ($\mathrm{\Delta }\alpha )$ and first hyperpolarizability (${\beta }_{\mathrm{\text{tot}}}$) values were calculated. The static first hyperpolarizability value is found to be six times higher than urea. Ultra violet-visible spectrum of DCBLPZ molecule was calculated by time-dependent density functional theory (TD-DFT) in gas phase using different functionals. The calculated value of absorption wavelength was found at 234nm using TD-B3LYP/$6\text{-}311++\mathrm{\text{G}}$* level of theory and was in good agreement with experimental value (230nm) than other applied methods. Our results give us flexibilty to predict about possible intramolecular charge transfer from both the chlorine atoms toward both the proline units through zinc atom in the studied metallic complex. The other important parametres such as frontier molecular orbital’s (FMO), global reactivity descriptors and molecular electrostatic potential have also been calculated and discussed.

This work explores the vibrational state-selective photoassociation (PA) in the ground state of the HX (X = F, Cl, I) molecule by solving the time-dependent Schrödinger equation. For the three systems, the vibrational level of $v=17$ is set to be the target state and the PA probability of the target state is calculated and compared by considering different initial collision momentums. It is found that the PA probabilities are in accordance with Franck–Condon overlap integral for the HI and HCl systems, but it is not the case for the HF system. Moreover, for the HF system, it is shown that the PA probability of the target state is largest and the multiphoton transition is more likely to occur.

The detached electron flux and photodetachment cross section are derived using the theoretical imaging method and quantum approach for system comprising of hydrogen negative ion ($H^{\mathrm{-}}$) placed near a surface having spherical dent. The dent is modeled like a spherical concave surface. It is observed that the spherical dent generates additional oscillatory and smooth structure in the detached electron flux and photodetachment cross section, respectively. The radius of curvature, inter-ion surface distance and the dent factor strongly manipulate the results. When the inter-ion surface distance is equal to the focal length of the concave surface, the detached electron flux and photodetachment cross section are not well behaved. The photodetachment cross section is also not well behaved for the inter-ion surface distance equal to the radius of curvature. The focus and center of curvature of the concave surface act as a spherical singularity. This study gives new understanding on the photodetachment of negative ions in the vicinity of concave surfaces.