scholarly journals Picosecond Anti-Stokes Raman Excitation Profiles as a Method for Investigating Vibrationally Excited Transients

1999 ◽  
Vol 19 (1-4) ◽  
pp. 335-341 ◽  
Author(s):  
Hiromi Okamoto ◽  
Takakazu Nakabayashi ◽  
Mitsuo Tasumi
Keyword(s):  
Vibrational Energy ◽  
Vibrational Modes ◽  
Vibrational States ◽  
Vibrationally Excited ◽  
Quantum Numbers ◽  
Trans Stilbene ◽  
Raman Process ◽  
Vibrationally Hot Molecules ◽  
Raman Excitation Profiles ◽  
Anti Stokes

A method for estimating vibrational quantum numbers of vibrationally excited transients in solution is proposed. In this method, we calculate anti-Stokes Raman excitation profiles (REPs) which are characteristic of the initial vibrational states involved in the Raman process, and compare them with observed anti-Stokes intensities. We have applied this method to vibrationally hot molecules of canthaxanthin in the So state and those of trans-stilbene in the S1 state. For canthaxanthin, it has been found that the vibrationally excited transients are for the most part on the ν=1 level of the C═C stretching mode, and that excess vibrational energy is statistically distributed among all intramolecular vibrational modes. As for S1 stilbene, vibrational transients are shown to be mostly on the ν=1 level for two vibrational modes examined, while the excess vibrational energy is probably localised on the olefinic C═C stretching mode.

scholarly journals Pump- And Probe-Wavelength Dependencies of Picosecond Anti-Stokes Raman Spectrum of Trans-Stilbene in the S1 State

1999 ◽  
Vol 19 (1-4) ◽  
pp. 75-78 ◽  
Author(s):  
Takakazu Nakabayashi ◽  
Hiromi Okamoto ◽  
Mitsuo Tasumi
Keyword(s):  
Vibrational Relaxation ◽  
Vibrational Energy ◽  
Wavelength Dependence ◽  
Relaxation Dynamics ◽  
Vibrationally Excited ◽  
Time Resolved ◽  
Probe Wavelength ◽  
Trans Stilbene ◽  
Pump And Probe ◽  
Anti Stokes

Vibrational relaxation dynamics of trans-stilbene in the S1 state immediately after photoexcitation is studied by picosecond time-resolved anti-Stokes Raman spectroscopy with several pump and probe wavelengths. Pump-wavelength dependence of the anti- Stokes spectrum indicates that, when pump photons with high excess energy (≈5200cm-1) are used, the anti-Stokes Raman bands at 0 ps delay time arise from vibrationally excited transients with excess vibrational energy not thermally distributed in the molecule. Probe-wavelength dependence suggests that the vibrationally excited transients at 0 ps are mostly on the lowest excited vibrational levels, as far as the olefinic C═C stretching and the C–Ph stretching modes are concerned. The vibrational relaxation process of S1trans-stilbene is discussed on the basis of the observed results.

scholarly journals Detection of vibrationally excited HC7N and HC9N in IRC +10216

2020 ◽  
Vol 640 ◽  
pp. L13 ◽  
Author(s):  
J. R. Pardo ◽  
C. Bermúdez ◽  
C. Cabezas ◽  
M. Agúndez ◽  
J. D. Gallego ◽  
...  
Keyword(s):  
Excited States ◽  
Density Ratio ◽  
Rotational Constant ◽  
Complete Characterization ◽  
Vibrational States ◽  
Vibrationally Excited ◽  
Carbon Chains ◽  
Quantum Numbers ◽  
Integer Quantum ◽  
Bending Modes

Observations of IRC +10216 with the Yebes 40 m telescope between 31 and 50 GHz have revealed more than 150 unidentified lines. Some of them can be grouped into a new series of 26 doublets, harmonically related with integer quantum numbers ranging from Jup = 54 to 80. The separation of the doublets increases systematically with J, that is to say, as expected for a linear species in one of its bending modes. The rotational parameters resulting from the fit to these data are B = 290.8844 ± 0.0004 MHz, D = 0.88 ± 0.04 Hz, and q = 0.1463 ± 0.0001 MHz. The rotational constant is very close to that of the ground state of HC9N. Our ab initio calculations show an excellent agreement between these parameters and those predicted for the lowest energy vibrationally excited state, ν19 = 1, of HC9N. This is the first detection, and complete characterization in space, of vibrationally excited HC9N. An energy of 41.5 cm−1 is estimated for the ν19 state. In addition, 17 doublets of HC7N in the ν15 = 1 state, for which laboratory spectroscopy is available, were detected for the first time in IRC +10216. Several doublets of HC5N in its ν11 = 1 state were also observed. The column density ratio between the ground and the lowest excited vibrational states are ≈127, 9.5, and 1.5 for HC5N, HC7N, and HC9N, respectively. We find that these lowest-lying vibrational states are most probably populated via infrared pumping to vibrationally excited states lying at ≈600 cm−1. The lowest vibrationally excited states thus need to be taken into account to precisely determine absolute abundances and abundance ratios for long carbon chains. The abundance ratios N(HC5N)/N(HC7N) and N(HC7N)/N(HC9N) are 2.4 and 7.7, respectively.

scholarly journals Observation of Intermode Coupling in the 3μm IR Multiple Photon Excitation of Propylene

1983 ◽  
Vol 1 (5) ◽  
pp. 177-183 ◽  
Author(s):  
R. L. Woodin ◽  
C. F. Meyer
Keyword(s):  
Energy Deposition ◽  
Excited Molecule ◽  
Vibrational Modes ◽  
Vibrational States ◽  
Vibrationally Excited ◽  
Laser Chemistry ◽  
Methyl Group ◽  
Photon Excitation ◽  
Deuterium Substitution

The mechanism of IR multiple photon excitation through the dense manifold of vibrational states, usually called the quasicontinuum, of a vibrationally excited molecule is one of the unresolved issues in the field of laser chemistry. The effects of deuterium substitution on propylene IR multiple photon excitation are used to identify the vibrational modes leading to efficient excitation. Optoacoustic energy deposition data show that for propylene, 3 μm multiple photon excitation occurs most efficiently at the methyl group, and furthermore that efficient methyl group excitation requires the CH group on the adjacent carbon. Thus 3 μm multiple photon excitation of propylene, while involving energy deposition directly into several spatially discrete intramolecular groups, is found to be enhanced by specific intramolecular couplings. Implications of this result for mechanisms of IR multiple photon excitation are discussed.

scholarly journals Ideal pairing of the Stokes and anti-Stokes photons in the Raman process

2021 ◽  
Vol 103 (3) ◽  
Author(s):  
Kishore Thapliyal ◽  
Jan Peřina
Keyword(s):  
Raman Process ◽  
Anti Stokes

scholarly journals Semiclassical calculations of the quadruple excited four-electron systems

2007 ◽  
pp. 33-44
Author(s):  
N. Simonovic ◽  
M. Predojevic ◽  
V. Pankovic ◽  
P. Grujic
Keyword(s):  
Energy Levels ◽  
Point Of View ◽  
Interstellar Space ◽  
Vibrational Modes ◽  
Electron Systems ◽  
Atomic Systems ◽  
Excited Atoms ◽  
Relative Contribution ◽  
Quantum Numbers ◽  
Semiclassical States

Highly excited atoms acquire very large dimensions and can be present only in a very rarified gas medium, such as the interstellar space. Multiply excited beryllium-like systems, when excited to large principal quantum numbers, have a radius of r ? 10 ?. We examine the semiclassical spectrum of quadruple highly excited four-electron atomic systems for the plane model of equivalent electrons. The energy of the system consists of rotational and vibrational modes within the almost circular orbit approximation, as used in a previous calculation for the triply excited three-electron systems. Here we present numerical results for the beryllium atom. The lifetimes of the semiclassical states are estimated via the corresponding Lyapunov exponents. The vibrational modes relative contribution to the energy levels rises with the degree of the Coulombic excitation. The relevance of the results is discussed both from the observational and heuristic point of view.

scholarly journals The calculation of TV, VT, VV, VV' − rate coefficients for the collisions of the main atmospheric components

1998 ◽  
Vol 16 (7) ◽  
pp. 838-846 ◽  
Author(s):  
A. S. Kirillov
Keyword(s):  
Experimental Data ◽  
Energy Transfer ◽  
Vibrational Energy ◽  
Relaxation Times ◽  
Atmospheric Composition ◽  
Rate Coefficients ◽  
Frequency Change ◽  
Vibrational Energy Transfer ◽  
Ion Chemistry ◽  
Vibrationally Excited

Abstract. The first-order perturbation approximation is applied to calculate the rate coefficients of vibrational energy transfer in collisions involving vibrationally excited molecules in the absence of non-adiabatic transitions. The factors of molecular attraction, oscillator frequency change, anharmonicity, 3-dimensionality and quasiclassical motion have been taken into account in the approximation. The analytical expressions presented have been normalized on experimental data of VT-relaxation times in N2 and O2 to obtain the steric factors and the extent of repulsive exchange potentials in collisions N2-N2 and O2-O2. The approach was applied to calculate the rate coefficients of vibrational-vibrational energy transfer in the collisions N2-N2, O2-O2 and N2-O2. It is shown that there is good agreement between our calculations and experimental data for all cases of energy transfer considered.Key words. Ionosphere (Auroral ionosphere; ion chemistry and composition). Atmospheric composition and structure (Aciglow and aurora).

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