Reproducing Deep Tunneling Splittings, Resonances, and Quantum Frequencies in Vibrational Spectra From a Handful of Direct Ab Initio Semiclassical Trajectories
Articolo
Data di Pubblicazione:
2013
Citazione:
Reproducing Deep Tunneling Splittings, Resonances, and Quantum Frequencies in Vibrational Spectra From a Handful of Direct Ab Initio Semiclassical Trajectories / R. Conte, A. Aspuru Guzik, M. Ceotto. - In: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS. - ISSN 1948-7185. - 4:20(2013 Oct 17), pp. 3407-3412. [10.1021/jz401603f]
Abstract:
A time-dependent semiclassical approach for vibrational spectra
calculations is shown to describe deep tunneling splittings, resonances, and quantum
frequencies in multidimensional multiwell systems, by propagating a very limited
number of classical trajectories. The approach is tested on ammonia by evolving eight
trajectories on a full-dimensional PES. Quantum effects are reproduced, and results are
in good agreement with time-independent quantum calculations. All the features are
maintained when ab initio “on-the-fly” dynamics is adopted, thus demonstrating that
precomputation of the PES can be avoided. The approach overcomes the typical scaling
issues of quantum mechanical techniques without introducing any simplifications nor
reductions of dimensionality of the problem. The proposed methodology is promising
for further applications to systems of major complexity.
Tipologia IRIS:
01 - Articolo su periodico
Keywords:
semiclassical; ab initio; on-the-fly; initial value representation; ammonia
Elenco autori:
R. Conte, A. Aspuru Guzik, M. Ceotto
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