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Updated: Mar 29, 2026

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
A Full Dimensionality Approach to Evaluate the Nonlinear Optical Properties of Molecules with Large Amplitude
Marc Garcia-Borràs1, Miquel Solà1, David Lauvergnat2
1Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus Montilivi, 17071 Girona, Catalonia, Spain.
Abstract:
Previously, a reduced dimensionality approach was used to determine the vibrational contribution to nonlinear optical properties for molecules with large amplitude anharmonic modes that takes into account tunneling between potential wells (Luis, J. M.; Reis, H.; Papadopoulos, M. G.; Kirtman, B. J. Chem. Phys.2009, 131, 034116). Here, the treatment is extended, again using ammonia as an example, to include the remaining modes at several approximate levels. It is shown that this extension is essential to obtaining the correct results. Our new approach fully accounts for tunneling and avoids possible convergence problems associated with the normal coordinate expansion of the potential energy surface in a single-well treatment. For accurate numerical values, a good treatment of electron correlation is required along with a flexible basis set including diffuse functions.
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