Isotope effects in the electronic spectra of ammonia from ab initio semiclassical dynamics

Abstract

Despite its simplicity, the single-trajectory thawed Gaussian approximation has proven useful for calculating vibrationally resolved electronic spectra of molecules with weakly anharmonic potential energy surfaces. Here, we show that the thawed Gaussian approximation can capture surprisingly well even more subtle observables, such as the isotope effects in the absorption spectra, and we demonstrate it on the four isotopologues of ammonia (NH${}_3$, NDH${}_2$, ND${}_2$H, ND${}_3$). The differences in their computed spectra are due to the differences in the semiclassical trajectories followed by the four isotopologues, and the isotope effects-narrowing of the transition band and reduction of the peak spacing-are accurately described by this semiclassical method. In contrast, the adiabatic harmonic model shows a double progression instead of the single progression seen in the experimental spectra. The vertical harmonic model correctly shows only a single progression but fails to describe the anharmonic peak spacing. Analysis of the normal-mode activation upon excitation provides insight into the elusiveness of the symmetric stretching progression in the spectra.

25 pages, 5 figures

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• Simulating Molecular Single Vibronic Level Fluorescence Spectra with ab initio Hagedorn Wavepacket Dynamics
• On the single-Hessian Gaussian wavepacket dynamics