Relative vibrational populations of triplet B5g , W 1u, B ′36− u states of N2 and the b 16+ g state of O2 are calculated for different altitudes of the high-latitude upper atmosphere during auroral electron precipitation. It is shown that collisional processes cause a wavelength shift in the distribution of relative intensities for 1PG 1v=3 sequence of N2. The calculation of relative population...

Vibrational relaxation is an important physical process in hypersonic flows. Activation of the vibrational mode affects the fundamental thermodynamic properties and finite rate relaxation can reduce the degree of dissociation of a gas. Low fidelity models of vibrational activation employ a relaxation time to capture the process at a macroscopic level. High fidelity, state-resolved models have b...

Using an electronic spectrum of I2, Deslanders table and Birge-Sponer plots, vibrational and electronic parameters were calculated. The vibrational frequency, anharmonicity constant, dissociation energy and the equilibrium dissociation energy for the ground state were found to be 221.103 cm, 0.0119 cm, 12189 cm and 12300.2 cm, respectively. The vibrational frequency, anharmonicity constant, dis...

Experiments explore the influence of different C-H stretching eigenstates of CH3D on the reaction of CH3D with Cl(2P3/2). We prepare the mid |110>|0>(A1,E), mid |200>|>0(E), and mid |100>|0> +nu3 +nu5 eigenstates by direct midinfrared absorption near 6000 cm(-1). The vibrationally excited molecules react with photolytic Cl atoms, and we monitor the vibrational states of the CH2D or CH3 radical ...

Some of us have recently reported in Science [1] vibrational cooling of translationally cold Cs2 molecules into the lowest vibrational level v = 0 of the singlet XΣg ground electronic state. Starting from a sample of cold molecules produced in a collection of vibrational levels of the ground state, our method was based on repeated optical pumping by laser light with a spectrum broad enough to e...

The study of the vibrational energy dependence of radiative and radiationless processes has been a rich field for experiment and theory alike [l-S]. Although a good deal of progress has been made in both areas, there are many aspects of the problem which remain unclear. One of the most important of these aspects is the relative importance of internal conversion and intersystem crossing in deter...

Quantum state resolved reactivity measurements probe the role of vibrational symmetry on the vibrational activation of the dissociative chemisorption of CH4 on Ni(111). IR-IR double resonance excitation in a molecular beam was used to prepare CH4 in three different vibrational symmetry components, A1, E, and F2, of the 2ν3 antisymmetric stretch overtone vibration as well as in the ν1+ν3 symmetr...

Time-resolved, electronically resonant, coherent anti-Stokes Raman scattering is used to prepare and interrogate vibronic coherences of molecular iodine in matrix Ar. Coherences that involve evolution on the excited B(P0u) state, firstand third-order coherences, decay in less than one vibrational period ~t,300 fs!. In contrast, as many as 200 vibrational periods of motion can be observed for Ra...

A theoretical study of the kinetic and mechanism of 3-aug-Cope rearrangement in gas phase was performed usingDET methods at B3LYP levels of theory with 6-3114iG(d,p) bass set at 298.I5K. Equilibrium moleculargeometries and harmonic vibrational frequencies of the reactant, transition state Did product were calculated. Then,rate constant and activation thermodynamics parameters were calculated an...