We present here a first principle theoretical study of vibrational spectral diffusion and hydrogen bond dynamics in deuterated non aqueous system (ammonia and methanol) under ambient as well as in supercritical conditions without using any empirical potential. The trajectories of the systems were generated by using ab initio molecular dynamics and time series analysis was done by using the wavelet method for various frequency calculations. It is found that although one-to-one relation does not exist between instantaneous frequency of an ND (ammonia) or OD (methanol) bond and the distance of its corresponding hydrogen bond, such a relation does hold on an average. We have also employed the dispersion correction term introduced by Grimme in our simulations and also compared it with our results having no dispersion corrections. The dynamics of spectral-diffusion is investigated by means of frequency time correlation and spectral hole dynamics calculations. The results we obtained are compared with the existing experimental findings.

Ab initio molecular dynamics study of non aqueous fluids: Cases of ammonia and methanol in ambient and supercritical conditions

247th National Meeting (2014)

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