Search results for "anharmonicity"
showing 10 items of 118 documents
Strong-coupling expansion for the anharomonic oscillators −d2/dx 2+x 2+λx 2N
1992
A perturbation expansion based on a modified and scaled harmonic oscillator combined with Pade extrapolation techniques has been used to determine the expansion of the ground-state energy in fractional and negative powers of the coupling constant, valid for large values of λ.
Benchmark Thermochemistry of the Hydroperoxyl Radical
2004
A theoretical estimation of the enthalpy of formation for the hydroperoxyl radical is presented. These results are based on CCSD(T)/aug-cc-pCV5Z calculations extrapolated to the basis-set limit with additional corrections. Anharmonic vibrational zero-point energies, scalar relativistic, spin -orbit coupling, and diagonal BornOppenheimer corrections are further used to correct the extrapolated term energies, as well as various empirical corrections that account for correlation effects not treated at the CCSD(T) level. We estimate that ¢fH° ) 3.66 ( 0.10 kcal mol -1 (¢fH° ) 2.96 ( 0.10 kcal mol -1 ) using several reaction schemes. Significantly, it appears to be necessary to include effects o…
Fast vibrational configuration interaction using generalized curvilinear coordinates and self-consistent basis
2010
In this paper, we couple a numerical kinetic-energy operator approach to the direct-vibrational self-consistent field (VSCF)/vibrational configuration interaction (VCI) method for the calculation of vibrational anharmonic frequencies. By combining this with fast-VSCF, an efficient direct evaluation of the ab initio potential-energy surface (PES), we introduce a general formalism for the computation of vibrational bound states of molecular systems exhibiting large-amplitude motion such as methyl-group torsion. We validate our approach on an analytical two-dimensional model and apply it to the methanol molecule. We show that curvilinear coordinates lead to a significant improvement in the VSC…
Femtosecond coherent anti-Stokes Raman-scattering polarization beat spectroscopy of I2–Xe complex in solid krypton
2006
Time-resolved coherent anti-Stokes Raman-scattering (CARS) measurements are carried out to study the interaction between xenon atom and iodine molecule in a solid krypton matrix. Interference between the CARS polarizations of the "free" and complexed iodine molecules is observed, while the quantum beats of the complex are not detected due to low concentration. Vibrational analysis based on the polarization beats yields accurate molecular constants for the I2-Xe complex. The harmonic frequency of the I2-Xe complex is found to be redshifted by 0.90 cm-1 when compared to the free I2, whereas the anharmonicity is approximately the same. The dephasing rate of the complex is found to be somewhat …
Behaviour of the non-linear optical material KTiOPO4in the temperature range 293-973 K studied by x-ray diffractometry at high resolution: alkaline d…
1999
The crystal structure of potassium titanyl phosphate, KTiOPO4 (space group Pna21), has been refined at room temperature, at 673 K, and at 973 K, by using accurate single-crystal x-ray diffraction techniques at high resolution (dmin = 0.35 A). The data show a large amount of anharmonic motion of the potassium ions, increasing with temperature. To describe this motion, two models are developed: a normal refinement including potassium anharmonic thermal displacement parameters, which describes the average motion of the alkaline sites, and another model in which the potassium sites are split within the harmonic approximation and the displacements of the potassium ions versus temperature are des…
Order-disorder evolution in solid solutions of the NLO material KTiOPO : K Rb TiOPO and K Rb TiOPO in the temperature range 293-973 K
2000
K0.88Rb0.12TiOPO4 and K0.465Rb0.535TiOPO4 solid solutions of the potassium titanyl phosphate (KTiOPO4, space group Pna21) family, are described at 293, 473, 673, 873 and at 973 K. Their high resolution structures are obtained by using accurate single-crystal X-ray diffraction techniques at high resolution, (sin A-1. Large anharmonic motion of alkaline ions increasing with temperature allows the evolution of the rubidium and potassium ions repartition in the two alkaline sites versus temperature. To describe this motion inducing ionic conductivity phenomenon and to determine accurately the order-disorder evolution, two alkaline site refinement models are developed and discussed. A thermodyna…
Behavior of gap solitons in anharmonic lattices
2017
International audience; Using the theory of bifurcation, we provide and find gap soliton dynamics in a nonlinear Klein-Gordon model with anharmonic, cubic, and quartic interactions immersed in a parametrized on-site substrate potential. The case of a deformable substrate potential allows theoretical adaptation of the model to various physical situations. Nonconvex interactions in lattice systems lead to a number of interesting phenomena that cannot be produced with linear coupling alone. By investigating the dynamical behavior and bifurcations of solutions of the planar dynamical systems, we derive a variety of exotic solutions corresponding to the phase trajectories under different paramet…
Molecular origin and hydration dependence of protein anharmonicity: an elastic neutron scattering study.
2010
Two main onsets of anharmonicity are present in protein dynamics. Neutron scattering on protein hydrated powders revealed a first onset at about 150 K and a second one at about 230 K (the so called dynamical transition). In order to assess the molecular origin of protein anharmonicity, we study different homomeric polypeptides by incoherent elastic neutron scattering, thus disentangling the contribution of different molecular groups in proteins. We show that methyl group rotations are the main contributors to the low temperature onset. Concerning the dynamical transition, we show that it also occurs in absence of side chains; however, the presence and mobility of side chains substantially i…
Extrapolation of water and formaldehyde harmonic and anharmonic frequencies to the B3LYP/CBS limit using polarization consistent basis sets
2010
The harmonic and anharmonic frequencies of fundamental vibrations in formaldehyde and water were successfully estimated using the B3LYP Kohn-Sham limit. The results obtained with polarization- and correlation-consistent basis sets were fitted with a two-parameter formula. Anharmonic corrections were obtained by a second order perturbation treatment (PT2). We compared the performance of the PT2 scheme on the two title molecules using SCF, MP2 and DFT (BLYP, B3LYP, PBE and B3PW91 functionals) methods combined with polarization consistent pc-n (n = 0, 1, 2, 3, 4) basis sets, Dunning’s basis sets (aug)-cc-pVXZ where X = D, T, Q, 5, 6 and Pople’s basis sets up to 6-311++G(3df,2pd). The influence…
Gas-Phase Vibrational Spectroscopy of the Hydrocarbon Cations l-C3H+, HC3H+, and c-C3H2+: Structures, Isomers, and the Influence of Ne-Tagging
2019
We report the first gas-phase vibrational spectra of the hydrocarbon ions C3H+ and C3H2+. The ions were produced by electron impact ionization of allene. Vibrational spectra of the mass-selected ions tagged with Ne were recorded using infrared predissociation spectroscopy in a cryogenic ion trap instrument using the intense and widely tunable radiation of a free electron laser. Comparison of high-level quantum chemical calculations and resonant depletion measurements revealed that the C3H+ ion is exclusively formed in its most stable linear isomeric form, whereas two isomers were observed for C3H2+. Bands of the energetically favored cyclic c-C3H2+ are in excellent agreement with calculated…