Spin–orbit effects in photodissociation of sodium iodide

Abstract

Articles you may be interested inQuartet states of the acetylene cation: Electronic structure calculations and spin-orbit coupling terms Extensive ab initio study of the valence and low-lying Rydberg states of BBr including spin-orbit coupling Photodissociation of alkyl and aryl iodides and effect of fluorination: Analysis of proposed mechanisms and vertical excitations by spin-orbit ab initio study Ab initio spin-orbit CI calculations of the potential curves and radiative lifetimes of low-lying states of lead monofluoride Ab initio configuration interaction calculations of the electronic binding energies, spin-orbit coupling matrix elements and transition dipole moments of NaI are presented. The results are used to construct adiabatic and diabatic representations of the 0 ϩ molecular states relevant to predissociation. The dynamics of photopredissociation is elucidated by multichannel time-dependent wave packet propagation in the diabatic representation. Specific features associated with the spatial and temporal evolution of the wave packet are ascribed to those observed in femtosecond pump-probe experiments. In particular, the rate of decay of the electronically excited NaI* complex is found to be in close agreement with time-resolved experimental studies. Partial photoabsorption cross sections for the production of iodine atoms in the ground ( 2 P 3/2 ) and excited ( 2 P 1/2 ) spin-orbit states are calculated and found to peak at excitation wavelengths of 322 and 263 nm, respectively, in accord with experimental data.

Nonadiabatic Trajectory Studies of NaI(H2O)n Photodissociation Dynamics

“…1 The diabatic-state electronic resonance coupling H 12 0 (R), obtained from the semiempirical VB calculations appears to have a more reasonable behavior than that of Zewail and co-workers, 5,7 in that it is exponential in the internuclear separation range R > 2.7 Å, in agreement with ab initio calculations. 11 The semiempirical VB theory value -0.06 eV of H 12 0 (R) at the crossing point is in rather good agreement with the accepted value -0.055 eV, for which there is a wide consensus, both theoretically and experimentally. 5,12,39,40 The secular equation is solved next for the two-state problem to yield the NaI adiabatic electronic ground (X 1 Σ + ) and first excited (A 1 Σ + ) states.…”

“…Figure 1) are in good agreement with multireference singly and doubly excited configuration interaction (MRCI) ab initio calculations by Sakai et al, 9 and more recent ones by Alekseyev et al that include spin-orbit coupling. 11 As expected, the first excited state exhibits a shallow well resulting from the avoided crossing of the ionic and covalent states. The gas-phase NaI Franck-Condon (FC) excitation energy predicted by our semiempirical VB model corresponds to a wavelength of 296 nm, which lies at the lower end of the experimental range of excitation wavelengths.…”

Experiment to Test Whether We Live in a Four-Dimensional Physical Space–Time

“…There exist experimental data displaying clearly the revival periodicity. (5)(6)(7)(8)(9)(10)(11) Two systems satisfy the above conditions, they are the quantum harmonic oscillator and the infinite square well. They will be considered in Sec.…”

“…There is a well documented experimental support of the phenomenon (5)(6)(7)(8)(9)(10)(11). For example in Ref.…”

Pump-Probe Photoionization Study of the Passage and Bifurcation of a Quantum Wave Packet Across an Avoided Crossing

“…Figure 1 depicts the pump-probe scheme and the relevant potential curves for femtosecond photoelectron spectroscopy of the excited-state wave packet dynamics. The adiabatic excited state features an extended well whose character changes from covalent at shorter distances to ionic at larger distances due to an avoided crossing with the ground state at 7 A [22,23]. In the diabatic representation, the same system is viewed as an ionic curve (here called V 1 ) intersecting a covalent curve (V 2 ), with an associated nonadiabatic interaction (V 12 ).…”