Ayan Datta

Structures and Chemical Properties of Silicene: Unlike Graphene

The discovery of graphene and its remarkable and exotic properties have aroused interest in other elements and molecules that form 2D atomic layers, such as metal chalcogenides, transition metal oxides, boron nitride, silicon, and germanium. Silicene and germanene, the Si and Ge counterparts of graphene, have interesting fundamental physical properties with potential applications in technology. For example, researchers expect that silicene will be relatively easy to incorporate within existing silicon-based electronics. In this Account, we summarize the challenges and progress in the field of silicene research. Theoretical calculations have predicted that silicene possesses graphene-like properties such as massless Dirac fermions that carry charge and the quantum spin Hall effect. Researchers are actively exploring the physical and chemical properties of silicene and tailoring it for wide variety of applications. The symmetric buckling in each of the six-membered rings of silicene differentiates it from graphene and imparts a variety of interesting properties with potential technological applications. The pseudo-Jahn-Teller (PJT) distortion breaks the symmetry and leads to the buckling in silicenes. In graphene, the two sublattice structures are equivalent, which does not allow for the opening of the band gap by an external electric field. However, in silicene where the neighboring Si atoms are displaced alternatively perpendicular to the plane, the intrinsic buckling permits a band gap opening in silicene in the presence of external electric field. Silicenes stronger spin orbit coupling than graphene has far reaching applications in spintronic devices. Because silicon prefers sp(3) hybridization over sp(2), hydrogenation is much easier in silicene. The hydrogenation of silicene to form silicane opens the band gap and increases the puckering angle. Lithiation can suppress the pseudo-Jahn-Teller distortion in silicene and hence can flatten silicenes structure while opening the band gap. So far, chemists have not successfully synthesized and characterized a free-standing silicene. But recently chemists have successfully produced silicene sheets and nanoribbons over various substrates such as silver, diboride thin films, and iridium. The supporting substrate critically controls the electronic properties of silicene, and the match of the appropriate support and its use is critical in applications of silicene.

Dipolar interactions and hydrogen bonding in supramolecular aggregates: understanding cooperative phenomena for 1st hyperpolarizability

Weak intermolecular forces like dipolar interactions and hydrogen-bonding lead to a variety of different packing arrangements of molecules in crystals and self-assemblies. Such differences in the arrangements change the extent of excitonic splitting and excitation spectra in the multichromophore aggregates. In this tutorial review, the role of such interactions in fine tuning the linear and 1st non-linear optical (NLO) responses in molecular aggregates are discussed. The non-additivity of these optical properties arise specifically due to such cooperative interactions. Calculations performed on dimers, trimers and higher aggregates for model systems provide insights into the interaction mechanisms and strategies to enhance the 1st hyperpolarizabilities of pi-conjugated molecular assemblies. Flexible dipole orientations in the alkane bridged chromophores show odd-even variations in their second-harmonic responses that are explained through their dipolar interactions in different conformations. Parameters for the optical applications of molecules arranged in constrained geometry, like in Calix[n]arene, have been elucidated. We also highlight the recent developments in this field of research together with their future prospects.

Dipole orientation effects on nonlinear optical properties of organic molecular aggregates

We consider a few dipolar organic molecules in several of their packing arrangements to understand the aggregation effect. We have performed an extensive semiempirical calculations based on multireference doubles configuration interactions for the dimer arrangements. This is coupled with a simple theory based on dipole–dipole interactions and hydrogen-bonding effects. We find that the best dimer configuration is the in-line head-to-tail arrangement of the monomer molecules, which gives rise to an enormous increase in nonlinear optical properties compared to its monomer counterparts, at small distances. We have also shown that such dimer configurations have an appreciable absorption intensity, and for an aggregate, the absorption appears deep in the IR region. These excitations are excitonic in character and are associated with a large dipole moment change, along the long axis of the dimer configurations. We suggest the experimental methods by which such tunings can be realized.

Molecular Balances Based on Aliphatic CH−π and Lone-Pair−π Interactions

CH···π and lone-pair···π interactions are estimated for a series of conformationally dynamic bicyclic N-aryliimides. On the basis of their strengths and mutual synergy/competition, the molecules prefer a folded/unfolded conformation. Calculations suggest strategies to selectively isolate the folded form by increasing the strength of the attractive CH···π interaction or removing the lone-pair···π repulsion. While the barrier for the folded ⇄ unfolded transformation is too large to conformationally lock the molecules in either of the conformers, the dynamics for hopping of the alkyl group across rings and tumbling over the rings are found to be facile in the folded conformation.

Electron and hole mobilities in polymorphs of benzene and naphthalene: role of intermolecular interactions.

The hole and electron mobilities of the polymorphs of benzene and naphthalene crystals are estimated through quantum chemical calculations. The reorganization energy (lambda) and the charge-transfer matrix elements (Hmn) calculated for the two molecules reveal that these crystals can be used for dual applications, for both hole and electron conductance. The electron mobilities are five to eight times more than the hole mobilities for benzene while for naphthalene, the hole mobilities are almost an order magnitude more than the electron mobilities. The transfer matrices for both hole and electron conductance decrease monotonically with increase in the intermolecular distances. Calculations for various unique stacked dimers as determined from the radial distribution functions in both the crystals for the two molecules show strong dependence on the orientations of the rings and for similar intermolecular separations; Hmnhole is larger than Hmnelectron. The crystal mobilities are calculated from the weighted average over all the unique pair of molecules. The overall preference in a crystal for hole or electron mobility depends on the mutual competition of lambdahole/lambdaelectron and Hmnhole/Hmnelectron. From our microscopic understanding of essential parameters, specific dimers are identified from the crystalline solids of the two polymorphs and experimental strategies are suggested to enrich such pairs in aggregates for enhancing mobilities for these organic solids.

Experimental evidence for heavy-atom tunneling in the ring-opening of cyclopropylcarbinyl radical from intramolecular 12C/13C kinetic isotope effects.

The intramolecular (13)C kinetic isotope effects for the ring-opening of cyclopropylcarbinyl radical were determined over a broad temperature range. The observed isotope effects are unprecedentedly large, ranging from 1.062 at 80 degrees C to 1.163 at -100 degrees C. Semiclassical calculations employing canonical variational transition-state theory drastically underpredict the observed isotope effects, but the predicted isotope effects including tunneling by a small-curvature tunneling model match well with experiment. These results and a curvature in the Arrhenius plot of the isotope effects support the recently predicted importance of heavy-atom tunneling in cyclopropylcarbinyl ring-opening.

High‐Mobility Field Effect Transistors Based on Supramolecular Charge Transfer Nanofibres

Self-assembled charge transfer supramolecular nanofibres of coronene tetracarboxylate (CS) and dodecyl substituted unsymmetric viologen derivative (DMV) behave as active channel in field effect transistors exhibiting high mobility. These devices work in ambient conditions and can regenerate in the presence of a single drop of water.

Designing molecular switches based on DNA-base mispairing.

Stabilization of unstable mispairs on protonation in a DNA sequence can result in a change in the sequence conformation. Such sequences are being actively used for the synthesis of pH-driven molecular switches that have applications in biological pH sensing. We have studied various conformations of different mispairs of bases and their protonated forms using density functional theory (DFT) at B3LYP/6-31+G(d) and M05-2X/6-31+G(d,p) levels. Both gas-phase and aqueous-phase calculations are reported. Solvent phase calculations were done using the PCM and the COSMO solvation model. Our results show that the criterion for the protonation of a particular base in a mispair is not just its higher proton affinity. The planarity of the structure is significantly important, and a planar structure is energetically preferred over a bent mispair. Our calculations also show that the stabilization gained through protonation for the A-C, A-G, and the C-C mispairs is substantial (~20.0 kcal/mol); therefore, these are good candidates for pH-driven molecular switches.

Nitroxyl radical plus hydroxylamine pseudo self-exchange reactions: tunneling in hydrogen atom transfer.

Bimolecular rate constants have been measured for reactions that involve hydrogen atom transfer (HAT) from hydroxylamines to nitroxyl radicals, using the stable radicals TEMPO(*) (2,2,6,6-tetramethylpiperidine-1-oxyl radical), 4-oxo-TEMPO(*) (2,2,6,6-tetramethyl-4-oxo-piperidine-1-oxyl radical), di-tert-butylnitroxyl ((t)Bu(2)NO(*)), and the hydroxylamines TEMPO-H, 4-oxo-TEMPO-H, 4-MeO-TEMPO-H (2,2,6,6-tetramethyl-N-hydroxy-4-methoxy-piperidine), and (t)Bu(2)NOH. The reactions have been monitored by UV-vis stopped-flow methods, using the different optical spectra of the nitroxyl radicals. The HAT reactions all have |DeltaG (o)| < or = 1.4 kcal mol(-1) and therefore are close to self-exchange reactions. The reaction of 4-oxo-TEMPO(*) + TEMPO-H --> 4-oxo-TEMPO-H + TEMPO(*) occurs with k(2H,MeCN) = 10 +/- 1 M(-1) s(-1) in MeCN at 298 K (K(2H,MeCN) = 4.5 +/- 1.8). Surprisingly, the rate constant for the analogous deuterium atom transfer reaction is much slower: k(2D,MeCN) = 0.44 +/- 0.05 M(-1) s(-1) with k(2H,MeCN)/k(2D,MeCN) = 23 +/- 3 at 298 K. The same large kinetic isotope effect (KIE) is found in CH(2)Cl(2), 23 +/- 4, suggesting that the large KIE is not caused by solvent dynamics or hydrogen bonding to solvent. The related reaction of 4-oxo-TEMPO(*) with 4-MeO-TEMPO-H(D) also has a large KIE, k(3H)/k(3D) = 21 +/- 3 in MeCN. For these three reactions, the E(aD) - E(aH) values, between 0.3 +/- 0.6 and 1.3 +/- 0.6 kcal mol(-1), and the log(A(H)/A(D)) values, between 0.5 +/- 0.7 and 1.1 +/- 0.6, indicate that hydrogen tunneling plays an important role. The related reaction of (t)Bu(2)NO(*) + TEMPO-H(D) in MeCN has a large KIE, 16 +/- 3 in MeCN, and very unusual isotopic activation parameters, E(aD) - E(aH) = -2.6 +/- 0.4 and log(A(H)/A(D)) = 3.1 +/- 0.6. Computational studies, using POLYRATE, also indicate substantial tunneling in the (CH(3))(2)NO(*) + (CH(3))(2)NOH model reaction for the experimental self-exchange processes. Additional calculations on TEMPO((*)/H), (t)Bu(2)NO((*)/H), and Ph(2)NO((*)/H) self-exchange reactions reveal why the phenyl groups make the last of these reactions several orders of magnitude faster than the first two. By inference, the calculations also suggest why tunneling appears to be more important in the self-exchange reactions of dialkylhydroxylamines than of arylhydroxylamines.

Calculations Predict Rapid Tunneling by Carbon from the Vibrational Ground State in the Ring Opening of Cyclopropylcarbinyl Radical at Cryogenic Temperatures

B3LYP/6-31G(d) calculations have been performed on the ring opening of cyclopropylcarbinyl radical 1 to 3-buten-1-yl radical 2. The dynamics of the reaction have been computed with canonical variational transition state theory (CVT), both with and without inclusion of small-curvature tunneling (SCT). The CVT + SCT calculations predict that 1 should undergo rapid and temperature-independent ring opening to 2 at cryogenic temperatures, by tunneling from the lowest vibrational level of 1.