Coding Solvation Workshop

Implementation of Analytical Third Derivatives for a Fully Polarizable QM/Classical Hamiltonian

Tommaso Giovannini (Scuola Normale Superiore, Pisa)
Marta Olszówka (Scuola Normale Superiore, Pisa)
Chiara Cappelli (Scuola Normale Superiore, Pisa)

We extend the three-layer fully polarizable QM/MM/PCM model based on
fluctuating charges (FQ) [1-5] (QM/FQ/PCM) to the analytical evaluation of
energy third derivatives with respect to electric/magnetic field and nuclear
coordinates, which are used to calculate Raman and Raman Optical Activity (ROA)
spectra. In the QM/FQ/PCM the MM portion is described with FQs, i.e point
charges that can vary in agreement with the Electronegativity Equalization
Principle (EEP) [6]. A third layer is considered and described by means of the
Polarizable Continuum Model (PCM) [7]. To test the implementation, the method
is applied to the Raman and ROA spectra of (R)-Methyloxirane and (S)-Methyl
Lactate in aqueous solution [8], for which our approach has already been proven
to reliably reproduce other optical properties [9,10].

[1] C. Cappelli, Int. J. Quantum Chem. 116, 1532–1542 (2016).
[2] Lipparini, F., Barone, V. J. Chem. Theory Comput. 7, 3711 (2011).
[3] Lipparini, F., Cappelli, C., Barone, V. J. Chem. Theory Comput. 8, 4153 (2012).
[4] Lipparini, F., Cappelli, C., Scalmani, G., De Mitri, N., Barone, V. J. Chem. Theory Comput. 8, 4270 (2012).
[5] Lipparini, F., Cappelli, C., Barone, V. J. Chem. Phys. 138, 234108 (2013).
[6] R.T. Sanderson. Science 114, 670-672 (1951).
[7] Tomasi, J., Mennucci, B., Cammi, R. Chem. Rev., 105, 2999-3094 (2005).
[8] T. Giovannini, M. Olszówka, F. Egidi, J. R. Cheeseman, G. Scalmani, C. Cappelli submitted.
[9] F. Lipparini, F. Egidi, C. Cappelli, V. Barone. J. Chem. Theory Comput. 9, 1880-1884 (2013).
[10] T. Giovannini, M. Olszówka, C. Cappelli, J. Chem. Theory Comput. 12, 5483-5492 (2016).