Search results for "Rotational transition"
showing 10 items of 25 documents
A Rotational Thermalization Model for the Calculation of Collisionally Narrowed Isotropic Raman-Scattering Spectra - Application to the Srs-N2 Q-Bran…
1986
Abstract A model for the calculation of collisionally narrowed isotropic. Raman scattering spectra is proposed. In this model, the rotational transition probabilities are calculated within the strong collision approximation, allowing the rotational energy transfer rates to be expressed in terms of the sole individual Q( J ) line broadening coefficients. These transfer rates satisfy both detailed balance principle and unitarity of the scattering matrix in contrast with most of the previous approaches. Under further approximation concerning the rotational distribution of the collisional frequency, simpler expressions for transfer rates are deduced, which do not satisfy necessarily both unitar…
Quantum-chemical determination of Born–Oppenheimer breakdown parameters for rotational constants: the open-shell species CN, CO+ and BO
2013
The quantum-chemical protocol for computing Born-Oppenheimer breakdown corrections to rotational constants in the case of diatomic molecules is extended to open-shell species. The deviation from the Born-Oppenheimer equilibrium rotational constant is obtained by considering three contributions: the adiabatic correction to the equilibrium bond distance, the electronic contribution to the moment of inertia requiring the computation of the rotational g-tensor, and the so-called Dunham correction. Values for the Born-Oppenheimer breakdown parameters of CN, CO+, and BO in their (2)sigma(+) electronic ground states are reported based on coupled-cluster calculations of the involved quantities and …
Gauge-origin independent calculation of magnetizabilities and rotational g tensors at the coupled-cluster level.
2007
An implementation of the gauge-origin independent calculation of magnetizabilities and rotational g tensors at the coupled-cluster (CC) level is presented. The properties of interest are obtained as second derivatives of the energy with respect to the external magnetic field (in the case of the magnetizability) or with respect to magnetic field and rotational angular momentum (in the case of the rotational g tensor), while gauge-origin independence and fast basis-set convergence are ensured by using gauge-including atomic orbitals (London atomic orbitals) as well as their extension to treat rotational perturbations (rotational London atomic orbitals). The implementation within our existing …
Controlling molecular alignment rephasing through interference of Raman-induced rotational coherence
2000
0021-9606; Quantum control over molecular alignment rephasing is experimentally investigated in gaseous CO2. The control process is achieved by illuminating the medium with a pair of pump-pulses separated in time by approximately an integer value of T0=1/8B(0), where B(0) is the rotational constant. Through a Raman-type process, each pulse alone produces rotational coherence leading to a periodic orientational anisotropy. It is the combination of the two pulses that yields to quantum interference, resulting in a modification of this anisotropy probed by a third delayed pulse. The effect is accurately analyzed for different time delays between the two pulses. A theoretical analysis supplies …
State-to-state vibrational and rotational energy transfer in CO2 gas from time-resolved raman-infrared double resonance experiments
1998
A time-resolved Raman–infrared double resonance technique was used to study collisional relaxation rates of vibrational and rotational energy levels in CO2 gas at 295 K. A pulsed Raman excitation populated a selected rovibrational initial state. Measurements of the rates of transfer from the pumped initial state into specific final states were carried out using time-resolved laser absorption spectroscopy. First, the transfer rates were determined for the five lower vibrational energy levels. In particular, it was confirmed that the rate of transfer between the two Fermi levels (1000) and (0200) is very small [(5.3±0.2)×104 Torr-1 s-1]. The rotational structure inside the (0200) vibrational …
Quantum-chemical calculation of Born–Oppenheimer breakdown parameters to rotational constants
2010
The paper describes how Born–Oppenheimer breakdown parameters for the rotational constants of diatomic molecules can be determined via quantum-chemical computations. The deviations from the Born–Oppenheimer equilibrium values are accounted for by considering the adiabatic correction to the equilibrium bond distances, the electronic contribution to the rotational constant via the rotational g tensor, and the so-called Dunham correction, which can be computed directly from a polynomial expansion of the potential curve around the equilibrium distance. Calculations for HCl, SiS, and HF demonstrate the accuracy that can be achieved in the theoretical treatment of the considered Born–Oppenheimer …
High-resolution stimulated Raman spectroscopy of O2
1992
Abstract The S S and O O branches of the fundamental vibrational band of molecular oxygen in its electronic ground state have been resolved for the first time in Raman spectroscopy. The spectra have been observed, at room temperature and low pressure, with a stimulated Raman scattering (S.R.S.) spectrometer including a multipass cell. From these accurate Raman data combined with microwave data, we have improved the values of the vibrational, rotational, spin-spin, and spin-rotation interactions constants in the v = 1 vibrational state. Moreover, Raman Q branches of the first and second hot-bands have been recorded, allowing us to determine a set of molecular parameters for the v = 2 and v =…
Dual-broadband rotational CARS modelling of nitrogen at pressures up to 9 MPa. II. Rotational Raman line widths
2002
International audience; Rotational coherent anti-Stokes Raman spectroscopy (CARS) is a well-established spectroscopic technique for thermometry at pre-combustion temperatures an atmospheric pressure. However, at pressures of several MPa, a previous investigation revealed large discrepancies between experimental data and the theoretical model. A re-evaluation has been made of these data (at room temperature and in the range 1.5-9 MPa) with two improvements to the spectral code. The first is the inclusion of an inter-branch interference effect, which is described in detail in Paper I. The second is the use of experimental S-1-branch Raman line widths measured at 295 K, with a temperature depe…
Double-modulation sideband spectroscopy: μ0 and μ33 of silicon tetrafluoride
1992
Abstract The linear Stark effect in the ν 3 fundamental of 28 SiF 4 has been investigated with IR-IR double resonance employing CO 2 laser sidebands at microwave modulation frequencies. The frequencies needed for the double-resonance experiment were generated from one laser line by a novel double-modulation technique. As a result, the parameter of the vibration-induced dipole moment was determined to μ 33 = −0.10288(56) D. For the centrifugal distortion moment in the ν 3 excited state the value μ 0 = 6.06(36) × 10 −7 D was found. From the Stark splitting in the vibrational ground state, μ 0 = 6.81(10) × 10 −7 was determined.