Vibrationally excited molecules

Pibel C D, Sirota E, Brenner J and Dai H L 1998 Nanosecond time-resolved FTIR emission spectroscopy monitoring the energy distribution of highly vibrationally excited molecules during collisional deactivation J. Chem. Phys. 108 1297-300... 

Okamoto H, Nakabayashi T and Tasumi M 1997 Analysis of anti-Stokes RRS excitation profiles as a method for studying vibrationally excited molecules J. Phys. Chem. 101 3488-93... 

Section III.C). Using a rotational temperature to characterize an ion source can be misleading, as the reactions used to form the ions of interest can be quite exothermic, producing vibrationally and even electronically excited ions. These degrees of freedom are more difficult to cool than rotations. Transitions from vibrationally excited molecules provide very useful information, if they can be identified and analyzed. Hot FeO (produced using 3% N2O in helium) has a... 

Vibrationally mediated photodissociation (VMP) can be used to measure the vibrational spectra of small ions, such as V (OCO). Vibrationally mediated photodissociation is a double resonance technique in which a molecule first absorbs an IR photon. Vibrationally excited molecules are then selectively photodissociated following absorption of a second photon in the UV or visible [114—120]. With neutral molecules, VMP experiments are usually used to measure the spectroscopy of regions of the excited-state potential energy surface that are not Franck-Condon accessible from the ground state and to see how different vibrations affect the photodissociation dynamics. In order for VMP to work, there must be some wavelength at which vibrationally excited molecules have an electronic transition and photodissociate, while vibrationally unexcited molecules do not. In practice, this means that the ion has to have a... 

The V (OCO) ion has a structured electronic photodissociation spectrum, which allows us to measure its vibrational spectrum using vibrationally mediated photodissociation (VMP). This technique requires that the absorption spectrum (or, in our case, the photodissociation spectrum) of vibrationally excited molecules differ from that of vibrationally unexcited molecules. The photodissociation spectrum of V (OCO) has an extended progression in the V OCO stretch, indicating that the ground and excited electronic states have different equilibrium V "—OCO bond lengths. Thus, the OCO antisymmetric stretch frequency Vj should be different in the two states, and the... 

Another light pulse of frequency comes at a time delay ta and interacts with the vibrationally excited molecules. The intensity of the probe light transmitted through the interface is modulated as a function of the delay. The modulation is Fourier-transformed to provide the frequency and phase of the vibrational coherence. 

Vibrational excitation by electron impact of the background neutrals is an important process, because it is a major cause of energy loss for the electrons [reactions SVl (SiH4 stretching mode), SV2 (SIHt bending mode), and HV in Table II]. Moreover, the density of the vibrationally excited molecules has been reported to be important [211]. However, information about reaction coefficients of vibrationally excited molecules is scarce [192]. Here, only the vibrational excitation of SiHa and Ht is included [212, 213]. 

The delay time between the pump and the probe laser pulses is usually very short in these experiments. The delay time is less than 5 ns when the pump and the probe laser pulses are the same, and the delay time is as long as several hundred nanoseconds when the pump and the probe laser pulses are from two different sources. The short delay time ensures that the fragments flying with different velocities are equally sampled before they leave the detection region. Since the delay time is much shorter than the lifetime of the excited molecules (.A ), most of these molecules do not dissociate into fragments when the probe laser pulse arrives. As a result, the probe laser can easily cause dissociative ionization of the vibrationally excited molecules due to their large internal energy. 

Experiments to measure the vibrational de-excitation of NO at a metal surface are much more challenging than those already described. One needs both a source of vibrationally-excited molecules as well as means of detecting the results of the scattering interaction, necessitating the use... 

The photolysis of Cr(CO)6 also provides evidence for the formation of both CO (69) and Cr(CO) species (91,92) in vibrationally excited states. Since CO lasers operate on vibrational transitions of CO, they are particularly sensitive method for detecting vibrationally excited CO. It is still not clear in detail how these vibrationally excited molecules are formed during uv photolysis. For Cr(CO)6 (69,92), more CO appeared to be formed in the ground state than in the first vibrational excited state, and excited CO continued to be formed after the end of the uv laser pulse. Similarly, Fe(CO) and Cr(CO) fragments were initially generated with IR absorptions that were shifted to long wavelength (75,91). This shift was apparently due to rotationally-vibrationally excited molecules which relaxed at a rate dependent on the pressure of added buffer gas. 

A small fraction of the molecules are in vibrationally excited states. Raman scattering from vibrationally excited molecules leaves the molecule in the ground state. The scattered photon appears at higher energy, as shown in Figure lb. This anti-Stokes-shifted Raman spectrum is always weaker than the Stokes-shifted spectrum, but at room temperature it is strong enough to be useful for vibrational frequencies less than about 1500 cm 1. The Stokes and anti-Stokes spectra contain the same frequency information. 

Sometimes the atoms (or molecules) in molecular beams are put into selected electronic, vibrational and rotational states. The initial state selection can be made with lasers. A laser beam of appropriate frequency is shined onto a molecular beam and the molecule goes onto an appropriate excited state. The efficiency of selection depends upon the absorption coefficient. We can attain sufficient absorption to get highly vibrationally excited molecule with the laser. A spin forbidden transition can also be achieved by using a laser. 

Henry, B. R. (1977), Use of Local Modes in the Description of Highly Vibrationally Excited Molecules, Acc. Chem. Res. 10, 207. 

Sibert, E. L. (1990), Variational and Perturbative Descriptions of Highly Vibrationally Excited Molecules, Inti. Rev. Phys. Chem. 9,1. 

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