Toward anharmonic computations of vibrational spectra for large molecular systems

The subtle interplay of several different effects makes the interpretation and analysis of experimental spectra in terms of structural and dynamic characteristics a very challenging task. In this context, theoretical studies can be very helpful, and this is the reason behind the rapid evolution of computational spectroscopy from a highly specialized research field toward a versatile and widespread tool. However, in the case of vibrational spectra of large molecular systems, the most popular approach still relies on a harmonic treatment, because of the difficulty to explore the multidimensional anharmonic potential energy surface. These can be overcome considering that, in many cases, the vibrational transitions are well localized and only some of them are observed experimentally. To this aim, the procedure for the simulation of vibrational spectra of large molecular systems beyond the harmonic approximation is discussed. The quality of system-specific reduced dimensional anharmonic approaches is first validated by comparison with computations taking into account all modes simultaneously for anisole and glycine. Next, the approach is applied to two larger systems, namely glycine adsorbed on a silicon surface and chlorophyll-a in solution, and the results are compared with experimental data showing significant improvement over the standard harmonic approximation. Our results show that properly tailored reduced dimension anharmonic approaches stand as feasible routes for state-of-the-art computational spectroscopy studies and allow to take into account both anharmonic and environmental effects on the spectra even for relatively large molecular systems. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012