Search results for "Vibrational spectroscopy"
showing 10 items of 85 documents
High-Resolution Spectroscopy and Structure of Osmium Tetroxide. A Benchmark Study on 192OsO4
2012
Osmium tetroxide (OsO(4)) is a heavy tetrahedral molecule that constitutes a benchmark for quantum chemistry calculations. Its favorable spin statistics (due to the zero nuclear spin of oxygen atoms) is such that only A(1) and A(2) (T(d) symmetry) rovibrational levels are allowed, leading to a dense but quite easily resolvable spectrum. We reinvestigate here the ν(1)/ν(3) stretching fundamental (940-980 cm(-1)) dyad region and perform new assignments and effective Hamiltonian parameter fits for the main isotopologue ((192)OsO(4)). We also investigate the ν(2)/ν(4) bending fundamental dyad (300-360 cm(-1)) for the first time and perform a preliminary analysis. New experimental data have been…
Extended Fourier-transform spectroscopy studies and deperturbation analysis of the spin-orbit coupled A1Σ+ and b3Π states in RbCs.
2014
The article presents a study of the strongly spin-orbit coupled singlet A(1)Σ(+) and triplet b(3)Π states of the RbCs molecule, which provide an efficient optical path to transfer ultracold molecules to their rovibrational ground state. Fourier-transform A(1)Σ(+) - b(3)Π → X(1)Σ(+) and (4)(1)Σ(+) → A(1)Σ(+) - b(3)Π laser-induced fluorescence (LIF) spectra were recorded for the natural mixture of the (85)Rb(133)Cs and (87)Rb(133)Cs isotopologues produced in a heat pipe oven. Overall 8730 rovibronic term values of A(1)Σ(+) and b(3)Π states were determined with an uncertainty of 0.01 cm(-1) in the energy range [9012, 14087] cm(-1), covering rotational quantum numbers J ∈ [6, 324]. An energy-ba…
Raman spectroscopy and crystal-field split rotational states of photoproducts CO and H2 after dissociation of formaldehyde in solid argon.
2012
Raman signal is monitored after 248 nm photodissociation of formaldehyde in solid Ar at temperatures of 9-30 K. Rotational transitions J = 2 ← 0 for para-H(2) fragments and J = 3 ← 1 for ortho-H(2) are observed as sharp peaks at 347.2 cm(-1) and 578.3 cm(-1), respectively, which both are accompanied by a broader shoulder band that shows a split structure. The rovibrational spectrum of CO fragments has transitions at 2136.5 cm(-1), 2138.3 cm(-1), 2139.9 cm(-1), and 2149 cm(-1). To explain the observations, we performed adiabatic rotational potential calculations to simulate the Raman spectrum. The simulations indicate that the splitting of rotational transitions is a site effect, where H(2) …
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 …
The partition sum of methane at high temperature
2008
11 pages, 4 Tables, 3 Figures Computer code on line at http://icb.u-bourgogne.fr/JSP/TIPS.jsp; International audience; The total internal partition function of methane is revisited to provide reliable values at high temperature. A multi-resolution approach is used to perform a direct summation over all the rovibrational energy levels up to the dissociation limit. A computer code is executable on line at the URL : http://icb.u-bourgogne.fr/JSP/TIPS.jsp to allow the calculation of the partition sum of methane at temperatures up to 3000 K. It also provides detailed information on the density of states in the relevant spectral ranges. The recommended values include uncertainty estimates. It is …
Theoretical absorption spectrum of the Ar–CO van der Waals complex
2003
The three-dimensional intermolecular electric dipole moment surface of Ar–CO is calculated at the coupled cluster singles and doubles level of theory with the aug-cc-pVTZ basis set extended with a 3s3p2d1f1g set of midbond functions. Using the rovibrational energies and wave functions of our recent study [J. Chem. Phys. 117, 6562 (2002)], temperature-dependent spectral intensities are evaluated and compared to available experimental data. Based on the theoretical spectrum, alternative assignments of the experimentally observed lines in the fundamental band of CO around 2160 and 2166 cm−1 are suggested. Thomas.Bondo@uv.es
Computational investigation and experimental considerations for the classical implementation of a full adder on SO2 by optical pump-probe schemes
2008
International audience; Following the scheme recently proposed by Remacle and Levine Phys. Rev. A 73, 033820 2006 , we investigate the concrete implementation of a classical full adder on two electronic states X˜ 1A1 and C ˜ 1B2 of the SO2 molecule by optical pump-probe laser pulses using intuitive and counterintuitive stimulated Raman adiabatic passage excitation schemes. The resources needed for providing the inputs and reading out are discussed, as well as the conditions for achieving robustness in both the intuitive and counterintuitive pump-dump sequences. The fidelity of the scheme is analyzed with respect to experimental noise and two kinds of perturbations: The coupling to the neigh…
C3v Top Data System (C3vTDS) software for spectrum simulation of XY3Z symmetric-top molecules using the group chain
2010
Abstract The C3v Top Data System (C3vTDS) program suite has been developed with the aim of studying any rovibrational band or polyad of XY3Z (C3v) symmetric-tops molecules in a singlet electronic state. It is developed in the same way as similar programs for various molecular symmetries (Td, Oh, C4v, C2v and D2h). We work in the O ( 3 ) ⊃ C ∞ v ⊃ C 3 v group chain and this choice has consequences on the method used to specify the input parameters for Hamiltonian and transition moment calculations. One example concerning the ν 2 band of the CH 3 12 D symmetric-top molecule is presented. This package consists in a series of FORTRAN programs called by scripts. The whole package is freely acces…
Extension of the MIRS computer package for the modeling of molecular spectra : from effective to full ab initio ro-vibrational hamiltonians in irredu…
2012
The MIRS software for the modeling of ro-vibrational spectra of polyatomic molecules was considerably extended and improved. The original version (Nikitin, et al. JQSRT, 2003, pp. 239--249) was especially designed for separate or simultaneous treatments of complex band systems of polyatomic molecules. It was set up in the frame of effective polyad models by using algorithms based on advanced group theory algebra to take full account of symmetry properties. It has been successfully used for predictions and data fitting (positions and intensities) of numerous spectra of symmetric and spherical top molecules within the vibration extrapolation scheme. The new version offers more advanced possib…
D2hTDS-ST Software for Stark Spectrum Simulation of X2Y4 Asymmetric-Top Molecules
2011
Abstract We present the D 2 h TDS-ST ( D 2 h -Top Data System for Stark effect) program suite with the aim to simulate Stark spectra of any IR active rovibrational polyad of X 2 Y 4 ( D 2 h ) asymmetric-top molecules. D 2 h TDS-ST consists in a series of FORTRAN programs called by scripts. For calculation of Stark spectra, we obtained the expressions of the dipole moment and polarizability operators of X 2 Y 4 molecules using a tensorial formalism. For convenience, we integrated the D 2 h TDS-ST programs into the D 2 h TDS package. The D 2 h TDS suite (including the D 2 h TDS-ST programs) is freely available at the URL: http://icb.u-bourgogne.fr/OMR/SMA/SHTDS/D2HTDS.html .