Study of highly vibrationally excited

McCoy A B and Siebert E L 1996 Canonical Van VIeck pertubation theory and its applications to studies of highly vibrationally excited states of polyatomic molecules Dynemics of Moiecuies end Chemicei Reections ed R E Wyatt and J Z H Zhang (New York Dekker) p 151... 

M. Silva, R. Jongma, R. W. Field, and A. M. Wodtke. The dynamics of stretched molecules experimental studies of highly vibrationally excited molecules with stimulated emission pumping. Annu. Rev. Phys. Chem., 52 811-852 (2001). 

Although work remains to be done on this problem, stimulated emission pumping (SEP) experiments strongly suggests the possibility of its occurrence. The SEP studies of highly vibrationally excited oxygen show a sharp increase in the disappearance of 02(v 26) when 02(v = 0) is the collision partner [114] and the existence of a dark channel above v = 25, where molecules prepared in a given vibrational state do not cascade down the vibrational ladder [115]. A second SEP experiment demonstrated that 02(v = 0) removes 02(v 26) at a rate 25-150 times faster than N2 [113], Subsequent studies revealed that other common atmospheric constituents such as C02 cannot compete with self-relaxation [116],... 

Canonical Van Vleck Perturbation Theory and Its Application to Studies of Highly Vibrationally Excited States of Polyatomic Molecules... 

Collisions of highly vibrationally excited molecules is eommonly a topie in the field of unimolecular reactions [1,2,3,4,5]. Collisions of vibrationally excited moleeules in that field are studied in the context of energy transfer, namely, when nonreaetive but inelastic collisions change the energy content of the moleeule that may undergo a unimolecular reaction. The possibility that the collisions of the exeited moleeules in the gas phase with reactive partners ean show specific phenomena has traditionally not been considered, exeept for diatomie moleeules. Bimolecular reaetions of vibrationally exeited moleeules have beeome a subjeet of intense study reeently, when experimental work indieated that a remarkable speed-up and state speeifieity ean be observed when simple moleeules in vibrationally exeited states collide with reactive partners [6,7,8, 9]. 

Hot electrons were also detected in the presence of molecular interactions or exothermic surface reactions at metal surfaces. Huang et al. [23, 33] studied the energy transfer of highly vibrationally excited molecules at surfaces and found efficient (>50 %) excitation of electrons in gold on the subpicosecond timescale by... 

Conventional spontaneous Raman scattering is the oldest and most widely used of the Raman based spectroscopic methods. It has served as a standard teclmique for the study of molecular vibrational and rotational levels in gases, and for both intra- and inter-molecular excitations in liquids and solids. (For example, a high resolution study of the vibrons and phonons at low temperatures in crystalline benzene has just appeared [38].)... 

Plenary 9. J W Nibler et al, e-mail address niblerj chem.orst.edu (CARS and SRS). High resolution studies of high lymg vibration-rotational transitions in molecules excited in electrical discharges and low density monomers and clusters in free jet expansions. Ionization detected (REMPI) SRS or IDSRS. Detect Raman... 

A recent study of the vibrational-to-vibrational (V-V) energy transfer between highly-excited oxygen molecules and ozone combines laser-flash photolysis and chemical activation with detection by time-resolved LIF [ ]. Partial laser-flash photolysis at 532 mn of pure ozone in the Chappuis band produces translationally-... 

In addition to the previously mentioned disadvantages, all of these methods have another drawback in the large molecule photofragment velocity measurements. For example, in the studies of UV photon photodissociation of polyatomic molecules, like alkene and aromatic molecules, molecules excited by the UV photons quickly become highly vibrationally excited in the ground electronic state through fast internal conversion, and dissociation occurs in the ground electronic state. 

An infrared chemiluminescence study [501] of the reaction 0(3P) + CH3 shows that it is direct with the formaldehyde product being highly vibrationally excited. A lower limit of (Fv) > 0.43 has been placed on this excitation. The high pressure reactions of 0(3P) atoms with various hydrocarbons show emission of vibrationally excited OH(d < 14) radicals which is attributed to the reaction [ 502]... 

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