Search results for "ROTATIONAL"
showing 10 items of 381 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…
A MRCI PS and CASSCF study of the ground state MgO dissociation energy
1991
Abstract Ab initio calculations at CASSCF and MRCI PS levels are used to determine the dissociation energy for the X 1 Σ + state of MgO, which adiabatically dissociates to the ground state 1 S g of magnesium and to the excited 1 D g state of oxygen, as well as other spectroscopic parameters. Emphasis is placed upon the problem of properly selecting an adequate active space in CASSCF calculations and upon the improvements obtained in MRCI by selecting perturbatively the most important contributions to the total wavefunction and evaluating the remaining ones only by perturbational method. Through a procedure based on stabilizing the computed dissociation energy, values of 3.87 eV (MRCI PS) an…
Size Dependence of Tracer Diffusion in Supercooled Liquids
1996
We have determined by forced Rayleigh scattering the diffusion coefficients D of several photochromic tracers with van der Waals radii between 0.38 and 8 nm (the largest ones being photolabeled polystyrene micronetworks) in 10 glass-forming liquids at temperatures between the glass temperature Tg and ∼1.2Tg. The results were analyzed in terms of power law plots, D(T) ∝ T/η(T)ξ, where η is the solvent shear viscosity, and temperature shifts, D(T) ∝ T/η(T + ΔT). The shift ΔT was related with the width of the rotational correlation time distribution via the time−temperature superposition principle.
The effect of temperature on the internal dynamics of dansylated POPAM dendrimers
2011
The internal and rotational dynamics of the dansylated poly(propylene amine) dendrimers (POPAM) have been studied by time correlated single photon counting (TCSPC) and molecular dynamics (MD) simulations. The hydrodynamic volumes of the dendrimer generations from G1 to G4 were estimated by fluorescence anisotropy data. Experiments and simulations suggest that the volume and the shape of the dendrimers are temperature dependent. At low temperatures the dendrimer structure becomes more spacious and rigid and back-folding of the individual branches is slowed down. For the G3 and G4 generations the temperature effects are much stronger than for the smaller G1 and G2 generations, where back-fold…
The equilibrium structure of trans-glyoxal from experimental rotational constants and calculated vibration–rotation interaction constants
2003
A total of six high-resolution FT-IR spectra for trans-glyoxal-d2, trans-glyoxal-d1 and trans-glyoxal-13C2 were recorded with a resolution ranging from 0.003 to 0.004 cm−1. By means of a simultaneous ground state combination difference analysis for each of these isotopologues using the Watson Hamiltonian in A-reduction and Ir-representation the ground state rotational constants are obtained. An empirical equilibrium structure is determined for trans-glyoxal using these experimental ground state rotational constants and vibration–rotation interaction constants calculated at the CCSD(T)/cc-pVTZ level of theory. The least-squares fit yields the following structural parameters for trans-glyoxal…
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…
Theoretical spectroscopic parameters of the alkali monofluorides LiF, NaF and KF
1992
Abstract Multireference configuration interaction and second-order perturbation theory are used to determine accurate spectroscopic parameters for the ground state of the alkali monofluorides from LiF to KF. Systematic saturation of the spdf subspaces of the atomic basis sets for the electron affinity of fluorine and the ionization potential of the metals have been shown to be more efficient than for the approximate dissociation energies in the molecule. the calculated rotational and vibrational constants and transitions for the three systems show excellent agreement with the expeirmental data.
Electrodes for REMPI spectroscopy in static gases and calculation of REMPI intensities: Application to molecular oxygen
1994
Resonance-enhanced multiphoton ionization (REMPI) of 16 O 2 X 3 Σ g − (ν = 0) through (3sσ g ) d'Π g (ν = 0) by using (2 + 1) one-colour photons is reported. This REMPI process, already observed and analysed by other authors at low pressure and low rotational temperature with mass spectrometry detection, is used to test our first detector of ionizations. Experimental difficulties have led to the design of an original arrangement of electrodes to collect electrons at room temperature and 1 Torr pressure of static molecular oxygen. A calculated spectrum is compared with the observed REMPI spectrum. The calculation uses the polarizability tensor and takes into account the competition between i…
Rotational spectrum and equilibrium structure of silanethione, H2SiS
2008
Unsubstituted silanethione, H(2)Si=S, has been characterized experimentally for the first time by means of rotational spectroscopy; the equilibrium structure of this fundamental molecule has been evaluated through a combination of experimental data from a total of ten isotopologues and results of high-level coupled-cluster calculations.
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) …