We report on a new approach to ease the computational overhead of ab initio "onthe-fly" semiclassical dynamics simulations for vibrational spectroscopy. The well known bottleneck of such computations lies in the necessity to estimate the Hessian matrix for propagating the semiclassical pre-exponential factor at each step along the dynamics. The procedure proposed here is based on the creation of a dynamical database of Hessians and associated molecular geometries able to speed up calculations while preserving the accuracy of results at a satisfactory level. This new approach can be interfaced to both analytical potential energy surfaces and on-thefly dynamics, allowing one to study even large systems previously not achievable.We present results obtained for semiclassical vibrational power spectra of methane, glycine, and N-acetyl-L-phenylalaninyl-L-methionine-amide, a molecule of biological interest made of 46 atoms.

Semiclassical (SC) vibrational spectroscopy is a technique capable of reproducing quantum effects (like zero-point energies, quantum resonances and anharmonic overtones) from classical dynamics runs even in the case of very large dimensional systems. In a previous work (R. Conte et al. J. Chem. Phys. 151, 214107 (2019))a preliminary sampling based on adiabatic switching (AS) has been shown to be able to improve precision and accuracy of semiclassical results for challenging model potentials and small molecular systems. In this manuscript we investigate the possibility to extend the technique to larger (bio)molecular systems whose dynamics must be integrated by means of ab initio "on-the-fly" calculations. After some preliminary tests on small molecules, we obtain the vibrational frequencies of glycine improving on pre-existing SC calculations. Finally, the new approach is applied to 17-atom proline, an amino acid characterized by a strong intramolecular hydrogen bond.

A set of permutationally invariant potential energy surfaces for the electronic ground state of formaldehyde is built at several levels of electronic theory and atomic orbital basis sets starting from a database of more than 34000 ab initio energies. Preliminarily, the reliability of the fitted surfaces is determined by comparing the calculated harmonic frequencies with the corresponding ab initio values. Then, semiclassical estimates of the quantum frequencies of vibration are presented, and their dependence on the employed level of theory, type of atomic orbital basis set, and complexity of the fit is investigated. Comparisons of semiclassical results to experimental data provide a further assessment of the quality of the analytical surfaces and show that anharmonic frequencies are influenced by the precision of the fit, while accurate frequency values are obtained also with density functional theory. Results and conclusions support the use of ab initio "on-the-fly" semiclassical dynamics as a means of spectroscopic investigation when high-level analytical potential energy surfaces are not available.

Proline, a 17-atom amino acid with a closed-ring side chain, has a complex potential energy surface characterized by several minima. Its IR experimental spectrum, reported in the literature, is of difficult and controversial assignment. In particular, the experimental signal at 3559 cm−1 associated with the OH stretch is interesting because it is inconsistent with the global minimum, trans-proline conformer. This suggests the possibility that multiple conformers may contribute to the IR spectrum. The same conclusion is obtained by investigating the splitting of the CO stretch at 1766 and 1789 cm−1 and other, more complex spectroscopic features involving CH stretches and COH/CNH bendings. In this work, we perform full-dimensional, on-the-fly adiabatically switched semiclassical initial value representation simulations employing the ab initio dft-d3-B3LYP level of theory with aug-cc-pVDZ basis set. We reconstruct the experimental spectrum of proline in its main features by studying the vibrational features of trans-proline and cis1-proline, and provide a new assignment for the OH stretch of trans-proline.

Anharmonic effects due to the shape of the molecular potential energy surface far from the equilibrium geometry are major responsible for the deviations of the actual frequencies of vibration from the harmonic estimates. However, anharmonic effects are not the solely responsible for this. Quantum nuclear effects also play a prominent role in theoretical vibrational spectroscopy as they contribute to drive away the molecular vibrational frequencies from their harmonic counterpart. The consequence of this is that anharmonicity and quantum effects may be difficult to separate spectroscopically and get often confused. In this work we show that anharmonicity can be detected by means of classical simulations, while quantum nuclear effects need to be identified by means of an approach originating from either the time independent or the time dependent Schroedinger equation of quantum mechanics. We show that classical methods are sensitive to the temperature or energy conditions under which they are undertaken. This leads to wrong frequency estimates, when dealing with few-Kelvin experiments, if one performs simulations simply matching the experimental temperature. Conversely, quantum approaches are not affected by this issue and they provide more and better information.