Desolvation Induced Conformational Transition in a Cryptophane Host: Crystal To Crystal Transformation.

Cryptophanes show different conformations in solution and solid state depending upon various factors, such as the length of connecting linkers, medium, and nature of the incoming guest molecule(s). A cyclotriguaiacylenes (CTG) based cryptophane molecule was synthesized using click chemistry containing three triazole linkers and studied as well. This molecule shows two conformations, out-out crown-crown (CC), and out-in CC, in the presence or absence of guest molecule(s), as studied both in solution and solid state. The out-in CC, in which both CTG fragments are in crown conformation with one crown sitting above the other, could be obtained by slow escape of the trapped acetone molecules from out-out CC in solid state. This transformation could be obtained through a single-crystal-to-single-crystal (SCSC) transformation from a large volume out-out CC to a smaller volume out-in CC conformation which is also supported by density functional theory calculations.

Maximally valent orbitals in systems with non-ideal bond-angles: atomic Wannier orbitals guided by the Mayer bond order.

In pursuit of a directed minimal set of basis for systems with non-ideal bond angles, in this work we find the exact orientation of the major overlapping orbitals along the nearest neighbouring coordination segments in a given system such that they maximally represent the covalent interactions throughout the system. We compute Mayer's bond order, akin to Wiberg's bond index, on the basis of atomic Wannier orbitals with customizable non-degenerate hybridization leading to variable orientations, constructed from first principles, in a representative variety of molecules and layered systems. We put such orbitals in perspective with unbiased maximally localized descriptions of bonding and non-bonding orbitals, and energetics to tunneling of electrons through them between nearest neighbours, to describe the different physical aspects of covalent interactions, which are not necessarily represented using a single unique set of atomic or bonding orbitals.

Hybrid Atomic Orbital Basis from First Principles: Bottom-Up Mapping of Self-Energy Correction to Large Covalent Systems.

Construction of hybrid atomic orbitals is proposed as the approximate common eigenstates of finite first moment matrices. Their hybridization and orientation can be a priori tuned as per their anticipated neighborhood. Their Wannier function counterparts constructed from the Kohn-Sham (KS) single particle states constitute an orthonormal multiorbital tight binding (TB) basis resembling hybrid atomic orbitals locked to their immediate atomic neighborhood, while spanning the subspace of KS states. The proposed basis thus renders predominantly single TB parameters from first principles for each nearest neighbor bond involving no more than two orbitals irrespective of their orientation and also facilitates an easy route for the transfer of such TB parameters across isostructural systems exclusively through mapping of neighborhoods and projection of orbital charge centers. With hybridized 2s, 2p and 3s, 3p valence electrons, the spatial extent of the self-energy correction (SEC) to TB parameters in the proposed basis is found to be localized mostly within the third nearest neighborhood, thus allowing effective transfer of self-energy-corrected TB parameters from smaller reference systems to much larger target systems, with nominal additional computational cost beyond that required for explicit computation of SEC in the reference systems. The proposed approach promises inexpensive estimation of the quasi-particle structures of large covalent systems with workable accuracy.

Transferability of self-energy correction in tight-binding basis constructed from first principles.

We demonstrate in this work the transferability of self-energy (SE) correction (SEC) of Kohn-Sham (KS) single particle states from smaller to larger systems, when mapped through localized orbitals constructed from the KS states. The approach results in a SE corrected TB framework within which the mapping of SEC of TB parameters is found to be transferable from smaller to larger systems of similar morphology, leading to a computationally inexpensive approach for the estimation of SEC in large systems with reasonably high accuracy. The scheme has been demonstrated in insulating, semiconducting, and magnetic nanoribbons of graphene and hexagonal boron nitride, where the SEC tends to strengthen the individual π bonds, leading to transfer of charges from the edge to bulk. Additionally, in magnetic bipartite systems, the SEC tends to enhance inter-sublattice spin separation. The proposed scheme thus promises to enable the estimation of SEC of bandgaps of large systems without the need to explicitly calculate the SEC of KS single particle levels, which can be computationally prohibitively expensive.