Abstract
The critical point is believed to be not amenable to quantum mechanical calculations because the correlation length goes to infinity, the density is largely inhomogeneous and some thermodynamic properties diverge. For these reasons, until very recently all theoretical information of the critical point has been obtained by statistical physics and nothing was known about the electronic structure. Employing a sequential quantum mechanical/molecular mechanical (S-QM/MM) approach for a nonpolar atomic fluid, we study the behavior of the dielectric constant at different temperatures, ranging from dense fluid to supercritical condition. Our primary focus lies on the vicinity of the critical point. By using quantum mechanical calculations with thermodynamic condition, we perfectly reproduce the behavior found previously for classical monoatomic fluid by using scaling functions and renormalization theory that in the vicinity of the critical point the dielectric constant shares the critical behavior of the internal energy and, although the dielectric constant remains finite, its variation with temperature diverges. This perfect agreement leads credence to multiscale QM/MM methods and suggests the possibility of obtaining theoretical information about the electronic structure of a fluid near the critical point.
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Acknowledgements
The authors thank CAPES for the BioMol project 23038.004630/2014-35; the National Institute of Science and Technology of Complex Fluids (INCT-FCx) with the CNPq Grant 141260/2017-3 and FAPESP Grant 2014/50983-3; TNR thanks a FAPESP Grant 2015/14189-3. KC and SC acknowledge CNPq for continuous support. This work is dedicated to Prof. Fernando R. Ornellas on the occasion of his 70th birthday.
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“Festschrift in honor of Prof. Fernando R. Ornellas” Guest Edited by Adélia Justino Aguiar Aquino, Antonio Gustavo Sampaio de Oliveira Filho & Francisco Bolivar Correto Machado.
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Bistafa, C., Ramos, T.N., Coutinho, K. et al. Quantum mechanics meets scaling theory near the critical point. Theor Chem Acc 139, 80 (2020). https://doi.org/10.1007/s00214-020-02596-x
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DOI: https://doi.org/10.1007/s00214-020-02596-x