Intermolecular V–V energy transfer in the photodissociation of CO2–HF(v=1)

Abstract

The Cr + -D 2 cation complex: Accurate experimental dissociation energy, intermolecular bond length, and vibrational parametersThe dissociation dynamics of HeI 35 Cl (B,v ′ =2,3) complexes with varying amounts of internal energy J. Chem. Phys. 122, 044318 (2005); 10.1063/1.1829971Rovibrational and dynamical properties of the hydrogen bonded complex ( CH 2 ) 2 S-HF : A combined free jet, cell, and neon matrix-Fourier transform infrared study Photofragment final state distributions have been measured for the vibrational predissociation of CO 2 -HF corresponding to excitation of the H-F stretching vibration. The method used in these studies combines photofragment translational spectroscopy, pendular state orientation methods, and laser probing to provide distributions that include the interfragment state correlations. The results clearly show that the dominant dissociation channel involves intermolecular V -V energy transfer corresponding primarily to excitation of the asymmetric stretching vibration of the CO 2 fragment. The dissociation energy of the complex has also been determined to be 672Ϯ4 cm Ϫ1 .

The state-to-state predissociation dynamics of OC–HF upon HF stretch excitation

“…2, which is in reasonably good agreement with experiment. This is in agreement with the previous systems we have studied 42,45,50 that also show that the electric field has no significant influence on the state-to-state dynamics.…”

“…7, which shows a comparison between the experimental angular distributions and the results of a purely statistical calculation, 47,48 the latter shown as the solid line. In the past 41,42,45,49 we have found much better agreement with a restricted phase space calculation, in which the two high frequency modes of the system, namely, the HF rotation and the CO vibration in this case, were constrained to agree with the experimental results. In this case, only the rotation of the heavy fragment and the translational degrees of freedom are treated statistically.…”

Spectroscopy and energetics of the acetylene molecule: dynamical complexity alongside structural simplicity

“…N 2 or C 2 H 2 scattered on one side of the incident molecular beam direction and HF on the other) and identified more reliably than is possible in zero field. Comparable PHOFAD studies of electrically oriented complexes have also been performed in the cases of CO 2 -HF [43,273], CO 2 -HCl [274], C 2 H 2 -HCl [39,43], OC-HF [43,275], and HCN-HF [43,276]. Oudejans and Miller have provided a critical tabular summary of complex dissociation energies D 0 , experimentally determined in molecular beams by various forms of translational spectroscopy including PHOFAD [43].…”

“…as considered in section 5 below). Such parallels have been discussed in the context of the PHOFAD of the linear CO 2 -HF complex [273]; in this case, the HF fragment appears at high values of rotational quantum number j and there is preferential population of vibrational modes that are parallel to the molecular axis (3) and (4) (3) and (4) Spectroscopy and energetics of the acetylene molecule 683 (including the 1 symmetric stretching mode of CO 2 , which has no transition-dipole coupling) [43,273].…”

Asymmetry in angular rigidity of hydrogen-bonded complexes

“…The intermolecular bending frequencies of both the proton donor and proton acceptor of a number of HF complexes are available from high-resolution laser spectroscopy of molecular beams or infrared absorption spectroscopy of matrix-isolated complexes. The spectral measurements at the vibrational excited states are frequently obtained as combination bands.The intermolecular bending frequencies ( D ) of HF, as proton donor, range from 271 cm Ϫ1 for N 2 -HF to 694 cm Ϫ1 for H 2 O-HF, as listed in Table 1 ( [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24]. For the strong hydrogen-bonded HF clusters, this vibration contributes the most to the zero-point energy of the complex.…”