Theory of electronic branching in the photodissociation of HI and DI

Abstract

Articles you may be interested inPhotodissociation of HI and DI: Testing models for electronic structure via polarization of atomic photofragments Electron attachment on HI and DI in a uniform supersonic flow: Thermalization of the electrons Potential curves, nonadiabatic couplings, and transition dipoles of the first four (3n I' 1 Ii 1,3n o , and 3l: I) excited electronic states of HI are extracted from various photodissociation experiments of HI in the near UV. Excellent agreement with these experiments regarding the overall absorption spectrum, the l*ep'/2)/lep3/2) branching ratio, and the {J anisotropies of the two channels at various wavelengths, has been achieved. On the basis of the electronic parameters thus extracted, the full dynamics of the HI photodissociation at all excitation energies in the near UV have been unravelled. The data obtained for HI is used to predict the photodissociation dynamics of 01. These predictions are in good agreement with available experimental results. Subsequent work will deal with prediction of the resonance Raman scattering ofHI/D1 and the control of the l*ep ,/2 )/lep3/2) branching ratio by elliptical control using the Asaro-Brumer-Shapiro scheme.

Photodynamic control using field optimized initial state: A mechanistic investigation of selective control with application to IBr and HI photodissociation

“…8 fall to zero much faster due to a quick dephasing of the wave packet in the coordinate space. Figure 9 contains the total absorption cross-sections obtained from the full Fourier transform of the autocorrelation function where the absorption spectrum with 0 as the initial states is once again in excellent agreement with experimental absorption profile for HI, 15 and Fig. 10 portrays the branching ratio ⌫͑I*/I͒ with 0 , 1 max and 2 max as the initial conditions.…”

“…6͑a͔͒ and nonadiabatic/ optical coupling elements used for our investigation of the HI photodissociation here are the same as those utilized earlier. 15,16,20 Probability density profiles from 0 , 1 , and 2 eigenfunctions included in the optimization manifold are plotted in Fig. 6͑b͒.…”

“…In any case, treatment of rotational effects will increase the computational complexities by at least an order of magnitude 37 and we have therefore found it judicious to neglect rotational motion in this initial application. Photodissociation of IBr 21,26,[38][39][40][41][42][43] and HI [9][10][11][12][13][14][15][16]20 have been studied extensively and are our representative systems of choice. In the following section we analyze some representative max (0) for IBr and HI to investigate the mechanistic underpinning of photodynamic control of product selectivity and yield.…”

“…1 While the focus of these theoretical approaches has been on field design, the photodissociation yield has also been found to be extremely sensitive to the initial vibrational state from which photolysis is induced. Examples include the photodissociation of H 2 ϩ , 13 D 2 ϩ , 14 HI, 15,16 HOD, 6,17,18 and HCl 19 in each of which the product yield has been found to be sensitive to the initial vibrational state of the molecule. Since the initial vibrational state which is subjected to photolysis is critical in determining the photodissociation products, it is reasonable to expect an appropriately optimized linear superposition of these vibrational eigenstates to serve as a better initial condition for selective maximization of the desired product.…”

High resolution time-of-flight spectrometer for crossed molecular beam study of elementary chemical reactions

“…The dynamics of HI photodissociation following at various wavelengths has been investigated previously using various experimental methods. [16][17][18][19][20][21][22][23][24][25] In order to characterize the apparatus, photodissociation of HI at 121.6 nm has been carried out. The purpose of the experiment is to characterize the detection laser system and the fixed long distance MCP detector.…”