A full-dimensional coupled-surface study of the photodissociation dynamics of ammonia using the multiconfiguration time-dependent Hartree method

作者：Giri Kousik; Chapman Emma; Sanz Cristina Sanz; Worth Graham^*

来源：Journal of Chemical Physics, 2011, 135(4): 044311.

DOI：10.1063/1.3614038

• ab initio calculations
• ammonia
• excited states
• ground states
• HF calculations
• infrared spectra
• isomerism
• molecule-photon collisions
• photodissociation
• potential energy surfaces
• ultraviolet spectra
• vibrational states
• visible spectra

Full-dimensional quantum mechanical computations are carried out to investigate the photodissociation dynamics of (A) over tilde state NH(3) and ND(3) using the multiconfiguration time-dependent Hartree (MCTDH) method with recently developed coupled ab initio potential energy surfaces (PESs) [Z. H. Li, R. Valero, and D. G. Truhlar, Theor. Chim. Acc. 118, 9 (2007)]. To use the MCTDH method efficiently the PESs are represented as based on the high-dimensional model representation. The (A) over tilde <- (X) over tilde absorption spectra for both isotopomers were calculated for the zeroth vibrational state of the ground electronic state. With a view to treating larger systems, Jacobi coordinates are used. Computations on the coupled PES are carried out for two-, three-, five-, and six-dimensional model systems to understand the validity of reduced-dimensional calculations. In addition to the fully coupled calculations, the effect of nonadiabatic coupling on absorption spectra is shown by propagating the initial wavepacket only in the (A) over tilde electronic state. The calculated absorption spectra are shown to be in good agreement with available theoretical and experimental observations. Comparisons with calculations using Radau and valence coordinates show the effect of including the symmetry of the system explicitly. Finally, branching ratios for loss of a hydrogen atom via the two available channels are calculated. These predict that the nonadiabatic product increases with the dimension of the calculations and confirm the importance of the full-dimensional calculations.

• 出版日期2011-7-28