Unveiling the theoretical aspects of superelectrophilic activation in an inverse demand Diels-Alder reaction.

The present computational study using B3LYP functional and 6-31+G(d) basis set has been accomplished to investigate the mechanism of the inverse demand Diels-Alder reaction between pyridyl imine and propene. The highly charged dicationic superelectrophilic diene with exceptionally low-lying LUMO makes the cycloaddition reaction with propene more favorable by significantly lowering the activation energy. The Wiberg bond indices are calculated in accordance with the formation and breaking processes of bonds. The synchronicity concept is also utilized to explain the global nature of the reaction. A potential outcome of this investigation is the utilization of propene as a C2 building block in the industry.

Superalkali-doped borazine and lithiated borazine complexes: diffuse excess electron and large first-hyperpolarizability.

A number of superalkali (M3O / M3S; M = Li, Na, K)-doped borazine and hexalithio borazine complexes are considered for the theoretical study of their electronic structure and quadratic polarizability. Electron-rich O/S atom of superalkali species remains very close to one boron atom of the ring through non-covalent interaction. The first-hyperpolarizability increases rather significantly upon superalkali doping. The chosen complexes possess diffuse excess electron which is located on the superpalkali moiety of borazine complexes and at the ring site of lithiated borazines. First-hyperpolarizability of M3O(S)@B3N3Li6 complexes are significantly larger than that of the corresponding M3O(S)@B3N3H6 complexes. The magnitude of first-hyperpolarizability of Li3S@B3N3Li6 is larger than that of Li3S@B3N3H6 by about three orders of magnitude.

Electronic structure and large second-order non-linear optical property of COT derivatives - a theoretical exploration.

A new strategy to design new molecules based on a fused hydrocarbon ring system comprising a COT ring and two 5-membered rings has been proposed for the study of second order NLO properties. The four charge transferring groups -NR2 (R = H, Li, Na and K) in conjunction with a sufficient number of electron withdrawing groups lead to significant variation of structural parameters and polarity. The charge transfer characteristics can be strongly modulated by introducing calcium metal atoms at suitable sites. Ca metal atoms end-capping the nitrogen ends of two adjacent -CN groups lead to electride character while a Ca metal atom bonded directly to the COT ring leads to greater charge transfer. The size of the alkali metal atom has been found to have a dramatic effect on the enhancement of first hyperpolarizability. The most significant electronic asymmetry induced by the larger potassium metal atom strongly enhances the magnitude of first hyperpolarizability. The variation of first hyperpolarizability has been satisfactorily explained in terms of TD-CAMB3LYP calculated spectroscopic parameters in light of the two-state model.

Erratum to: First hyperpolarizability of cyclooctatetraene modulated by alkali and alkaline earth metals.

The original version of this article unfortunately contained a mistake. Schemes I and II were missing. These important components are given below.

First hyperpolarizability of cyclooctatetraene modulated by alkali and alkaline earth metals.

In the present investigation, the first hyperpolarizability of alkali and alkaline earth metal derivatives of cyclooctatetraene (COT) has been calculated using BHHLYP and CAM-B3LYP functional for 6-311++G(d,p), 6-311++G(3df,3pd), and aug-pc 2 basis sets. Introduction of Na/K atoms at the axial position of COT and Li, Na, K/Be, Mg, Ca metal atoms and cyanide groups at the equatorial sites leads to lager enhancement of first hyperpolarizability. The ring charge density can account for the variation of first hyperpolarizability. The two state model has been invoked to explain the variation of first hyperpolarizability.

Successive lithiation of acetylene, ethylene and benzene: a comprehensive computational study of large static second hyperpolarizability.

This work is a revisit of the study of the electron correlation effect of lithium substitution on the second hyperpolarizability (106 a.u.) of acetylene, ethylene and benzene. The large quenching of mean second hyperpolarizability has been addressed by CCSD calculations. The inclusion of triple excitation in the MP4 method generally overestimates second hyperpolarizability in comparison to the MP4SDQ method. The present CCSD γav value of C6Li6: 405 × 104 a.u. obtained with a relatively larger basis set established the earlier prediction of Sadlej et al. [Phys. Chem. Phys. Chem., 2000, 2, 3393-3399] where degenerate non-dipolar transitions in low lying excited states play the crucial role. The successive lithiation results in gradual red shifting of transition energy leading to significant enhancement of second hyperpolarizability. Most of the chosen DFT functionals predict the correct qualitative trend of second hyperpolarizability. The quantitatively different results may be attributed to the case when the ground state wave function cannot be approximated by a single SD.