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Role of Tailor-Made Additives in Controlling Vapour Growth Asymmetry Along Polar Axis of α-Resorcinol Crystal: A Molecular-scale Study

Abstract

We report a mechanistic approach to study the effect of different tailor-made additives and conformers of resorcinol to elucidate the mechanism of unidirectional vapour growth of α-resorcinol crystal along polar axis. Based on the kinetics of the growth process, we derived an expression for rate of growth that eventually relates kinetic and thermodynamic aspect of the adsorption of host and additives molecules on flat-faces of crystals. Ab initio periodic dispersion corrected density functional theory using hybrid exchange-correlation functional has been employed to obtain adsorption energy landscape of the host molecule, different conformers of resorcinol and tailor-made auxiliaries to ascertain the role played by these auxiliaries towards understanding the growth anisotropy. Different steps configurations along 2-D lattice vectors and molecular orientations has been examined before obtaining adsorption energy of the host and tailor-made molecular auxiliaries. The results of our periodic density functional theory calculations show that the phenomena of asymmetric growth of α-resorcinol occurs because of the conformational change which arises due to the surface stabilization of the slower growing face. The calculated vapour growth anisotropy of the faces at the opposite ends of the polar axis of α-resorcinol is in excellent agreement with the experimental observation. We find that the adsorption energies of the strongly bind additives moieties such as 2-methylresorcinol, 5-methylresorcinol, phloroglucinol and hydroquinone at surface of faster growing (0-1-1) face are higher than that of the slower growing (011) face. It is thus, expected that vapour growth anisotropy decreased with an increase of the concentration of aforementioned molecular auxiliaries. On the other hand, admixture of β and γ-phase conformers of resorcinol and pyrogallol strongly interact with the slower growing face and, therefore, addition of these auxiliaries would increase the growth anisotropy. The results show that the vapour growth asymmetry decreases with increasing saturation temperature of β and and γ-phase conformers and pyrogallol deliberately added during crystallization. However, admixture of 2-methylresorcinol, 5-methylresorcinol, phloroglucinol and hydroquinone would result in increase of growth anisotropy with an increase of saturation temperature.

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Publication details

The article was received on 25 Jan 2018, accepted on 04 May 2018 and first published on 09 May 2018


Article type: Paper
DOI: 10.1039/C8CE00118A
Citation: CrystEngComm, 2018, Accepted Manuscript
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    Role of Tailor-Made Additives in Controlling Vapour Growth Asymmetry Along Polar Axis of α-Resorcinol Crystal: A Molecular-scale Study

    M. K. Singh and A. Banerjee, CrystEngComm, 2018, Accepted Manuscript , DOI: 10.1039/C8CE00118A

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