Md. Mehboob Alam

Cd(II) based metal–organic framework behaving as a Schottky barrier diode

A metal-organic framework (MOF) of cadmium(ii) is reported here which is the first example of an experimentally achieved MOF based electronic device, and in the present case it is a Schottky diode.

High-Polarity Solvents Decreasing the Two-Photon Transition Probability of Through-Space Charge-Transfer Systems - A Surprising In Silico Observation.

In the Letter, we address the question as to why larger two-photon absorption cross sections are observed in nonpolar than in polar solvents for through-space charge-transfer (TSCT) systems such as [2,2]-paracyclophane derivatives. In order to answer this question, we have performed ab initio calculations on two well-known TSCT systems, namely, a [2.2]-paracyclophane derivative and a molecular tweezer-trinitrofluorinone complex, and found that the two-photon transition probability values of these systems decreases with increasing solvent polarity. To rationalize this result, we have analyzed the role of different optical channels associated with the two-photon process and noticed that, in TSCTs, the interference between the optical channels is mostly destructive and that its magnitude increases with increasing solvent polarity. Moreover, it is also found that a destructive interference may sometimes even become a constructive one in a nonpolar solvent, making the two-photon activity of TSCTs in polar solvents less than that in nonpolar solvents.

A critical theoretical study on the two-photon absorption properties of some selective triaryl borane-1-naphthylphenyl amine based charge transfer molecules

In the present work, we have studied the two-photon absorption (TPA) properties of some selective molecules containing triarylborane and 1-naphthylphenylamine as the acceptor and donor moiety, respectively. The calculations are performed by using the state-of-the-art linear and quadratic response theory in the framework of the time dependent density functional theoretical method. The TPA parameters are calculated with CAMB3LYP functional and the cc-pVDZ basis set. The one-photon results indicate that both the electronic transitions (S(0)-S(1) and S(0)-S(2)) are associated with the charge transfer interaction between the donor and acceptor moieties along with the reorganization of the π-electron density. All these chromophores are found to have very strong two-photon active modes. In order to find out the origin of large TP transition probability of these molecules, we have performed two-state model (TSM) and sum-over-states (SOS) calculations. We have found that the TSM failed to reproduce the correct trend of the TP transition probability of the molecules obtained from the response theory, while SOS is quite successful in doing so. The whole study indicates that the transition moments between the excited states play a pivotal role in controlling the TP transition probabilities of these molecules. The role of solvent in the TP transition probability of these molecules has meticulously been scrutinized within the polarized continuum model (PCM). Further more, we have benchmarked our theoretical findings by calculating the TPA cross-section of a boron and nitrogen containing a charge transfer molecule for which the experimental result is available and we found that our theoretical result is in good agreement with the experimental one which definitely demonstrates the potential of all these light-emitting diode molecules as TP active materials too.

New design strategy for the two-photon active material based on push-pull substituted bisanthene molecule.

In the present work, we have critically examined the origin of strong two-photon transition probability of a donor-acceptor substituted bisanthene molecule that imitates a small piece of edge passivated (4, 4) graphene nanoribbon. In our calculations, we have considered -OMe, and -NH(2) as donors and -NO(2) as an acceptor. The one- and two-photon absorption parameters are evaluated using state-of-the-art linear and quadratic response theory, respectively, and all these calculations are carried out within the framework of time dependent density functional theory. To give a proper judgment on our findings, we have used the long-range corrected CAMB3LYP functional for all of the time dependent calculations. The present investigation reveals that the bisanthene molecule with three pairs of donor/acceptor moiety has a lower two-photon transition probability than that of a suitably designed bisanthene with only a single pair of donor/acceptor moiety. This in silico observation is consistent for all of the donor/acceptor moieties chosen in the present work. A comprehensive analysis at the two state model level of theory clearly offers us a verdict that by placing the donor/acceptor moiety in a suitable position of bisanthene, we can create a significant asymmetry in the electron density in the first excited state, which eventually leads to a significant difference in the ground and excited state dipole moment and is attributed to the higher two-photon transition probability of a particular bisanthene with a single pair of donor/acceptor moiety than bisanthene with three pairs of donor/acceptor.

The role of relativity and dispersion controlled inter-chain interaction on the band gap of thiophene, selenophene, and tellurophene oligomers.

Ab initio relativistic density functional theoretical calculations have been carried out on π-conjugated oligomers of increasing length with S, Se, and Te as heteroatoms. The band gap of the corresponding polymers has been obtained by plotting lowest unoccupied molecular orbital (LUMO)-highest occupied molecular orbital (HOMO)gap against the reciprocal of the number of monomer units (1/N) and extrapolating the curve to 1/N = 0. With B3LYP functional, we predict that role of relativistic correction terms is not very significant in the determination of final band gap of thiophene, selenophene, and tellurophene polymer. The origin of this observation is provided through the density of states (DOS) analysis which manifests that DOS contribution across the Fermi level of these polymers is mostly governed by C atoms and as a consequence relativistic correction terms due to heavy heteroatom remain insignificant to the band gap modification. We also inspected the role of inter-chain interaction in determining the net LUMO-HOMO gap of π-stacked double chain oligomers of increasing length. We have found that due to the exciton splitting in the stacked configurations, the LUMO-HOMO gap decreases steadily. Furthermore, we have noticed that dispersion force has important role in the reduction of the LUMO-HOMO gap of the oligomers studied.

Enhancement of Twist Angle Dependent Two-Photon Activity through the Proper Alignment of Ground to Excited State and Excited State Dipole Moment Vectors

Herein, we show that the two-photon (TP) transition probability (δTP) of o-betaine system will reach its maximum value at a twist angle around 65°. However, the potential energy scan with respect to the twist angle between its two rings indicates that the molecule in its ground state is quite unstable at this twist angle. Out of the different possibilities, the one having a single methyl group at the ortho position of the pyridinium ring is found to attain the optimum twist angle between the two rings, and interestingly, this particular substituted o-betaine has larger δTP value than any other substituted or pristine o-betaine. The twist angle dependent variation of δTP has been explained by employing the generalized-few-state-model formula for 3D molecules. The results clearly reveal that the magnitude of ground to excited state and excited state dipole moment vectors as well as the angle between them are strongly in favor of maximizing the overall δTP values at the optimum twist angle. The constructive interference between the optical channels at the optimum twist angle also plays an important role to achieve the maximum δTP value. Furthermore, to give proper judgment on our findings, we have also performed solvent phase calculations on all the model systems in nonpolar solvents, namely, cyclohexane and n-hexane, and the results are quite consistent with the gas phase findings. The present study will definitely offer a new way to synthesize novel two-photon active material based on o-betaine.

Effect of donor–acceptor orientation on solvent-dependent three-photon activity in through-space charge-transfer systems – case study of [2,2]-paracyclophane derivatives

We study the effect of donor-acceptor orientation on solvent-dependent three-photon transition probabilities (δ(3PA)) of representative through-space charge-transfer (TSCT) systems, namely, doubly positively charged [2,2]-paracyclophane derivatives. Our cubic response calculations reveal that the value of δ(3PA) may be as high as 10(6) a.u., which can further be increased by a specific orientation of the donor-acceptor moieties. To explain the origin of the solvent cum orientation dependency of δ(3PA), we have calculated different three-photon tensor components using a two-state model, noting that only a few tensor elements contribute significantly to the overall δ(3PA) value. We show that this dependence is due to the large dipole moment difference between the ground and excited states of the systems. The dominance of a few tensor elements indicates a synergistic involvement of π-conjugation and TSCT in the large δ(3PA) of these systems.

Channel interference in multiphoton absorption

We extend the theory of channel interference to higher-order multiphoton absorption processes. We derive an explicit expression for channel interference in a three-photon absorption process and propose a general scheme for deriving such expressions for multiphoton absorption processes of any order. Based on this general scheme, we derive and analyze the simplest few-state models for multiphoton absorption in centrosymmetric molecules and discuss the criteria for maximizing the corresponding multiphoton absorption strengths.

Electrically Controlled Eight‐Spin‐Qubit Entangled‐State Generation in a Molecular Break Junction

The generation of spin-based multi-qubit entangled states in the presence of an electric field is one of the most challenging tasks in current quantum-computing research. Such examples are still elusive. By using non-equilibrium Greens function-based quantum-transport calculations in combination with non-collinear spin density functional theory, we report that an eight-spin-qubit entangled state can be generated with the high-spin state of a dinuclear Fe(II) complex when the system is placed in a molecular break junction. The possible gate operation scheme, gating time, and decoherence issues have been carefully addressed. Furthermore, our calculations reveal that the preservation of the high spin state of this complex is possible if the experimentalists keep the electric-field strength below 0.78 V nm(-1). In brief, the present study offers a unique way to realize the first example of a multi-qubit entangled state by electrical means only.

Chemical control of a molecular spin switch in the presence of a gate

We predict that the electric field induced spin-crossover in a double –NO2 substituted Fe(II) complex will commence at the gate voltage, VG = −1.04 V and across this critical VG, the low and high spin states behave as “off” and “on” state, respectively which paves a unique way to realize an electronic spin switch controlled by a gate.