Search results for "Force constant"
showing 9 items of 9 documents
Vibrational spectra and force constants of symmetric tops
1983
The infrared spectrum of H3SiI in the 800–1050 cm-1 region has been recorded with a resolution of 0·04 cm-1 and rotationally analysed. Features related to the Fermi resonance between v 5 and v 3 + v 6 and to the Coriolis x, y resonance between v 2 and v 5 have been explained, and a set of vibration-rotation parameters for the three bands has been determined by least-squares calculations, σ(J, K) = 9·4 × 10-3 cm-1. The Fermi resonance matrix element |W 356| is found to be 3·7859(7) cm-1 and the vibrational frequencies are v 2 0 = 904·551(1), v 5 0 = 941·0746(8) and (v 3 + v 6)0 = 953·688(3) cm-1. The anharmonicity constant, x 36 = -1·745(9) cm-1, has been determined. Comparison is made with …
Étude théorique de la dynamique du réseau de PbTiO3 dans la phase quadratique
1999
Resume La dynamique du reseau du titanate de plomb PbTiO 3 est etudiee en phase quadratique a l'aide d'un modele a coquille tenant compte des polarisabilites electroniques des ions de la maille elementaire et des interactions a longue et a courte portee. Les resultats de nos calculs mettent en evidence le role important joue par l'anisotropie de la polarisabilite electronique de l'oxygene. Il est montre aussi que les courbes de dispersion des phonons calculees dans la premiere zone de Brillouin sont en bon accord avec l'experience.
Analytic CCSD(T) second derivatives
1997
A general-purpose implementation of analytic CCSD(T) second derivatives is presented. Its applicability is demonstrated by calculations of vibration-rotation interaction constants for the astrophysically important molecule cyclopropenylidene (C3H2) in which the required cubic force constants have been determined by numerical differentiation of analytically evaluated second derivatives of the energy.
On the determination of the intramolecular potential energy surface of polyatomic molecules: Hydrogen sulfide and formaldehyde as an illustration
2009
International audience; We present here an approach for determining the Hamiltonian of polyatomic molecules that allows one to successfully solve the problem of potential energy surface (PES) determination via construction and diagonalization of a Hamiltonian matrix of large dimension. In the suggested approach, the Hamiltonian is very simple and can be used both for any "normal" polyatomic molecule and for any isotopic species of a molecule. Molecules with two to four equivalent X-Y bonds are considered, and for illustration of the efficiency of the suggested approach, numerical calculations are made for the three-atomic (hydrogen sulfide) and four-atomic (formaldehyde) molecules.
A theoretical study of the 1B2u and 1B1u vibronic bands in benzene
2000
The two lowest bands, 1B2u and 1B1u, of the electronic spectrum of the benzene molecule have been studied theoretically using a new method to compute vibronic excitation energies and intensities. The complete active space (CAS) self-contained field (SCF) method (with six active π-orbitals) was used to compute harmonic force field for the ground state and the 1B2u and 1B1u electronic states. A linear approximation has been used for the transition dipole as a function of the nuclear displacement coordinates. Derivatives of the transition dipole were computed using a variant of the CASSCF state interaction method. Multiconfigurational second-order perturbation theory (CASPT2) was used to obtai…
The Reduction Pathway of End-on Coordinated Dinitrogen. II. Electronic Structure and Reactivity of Mo/W−N2, −NNH, and −NNH2 Complexes
2001
DFT calculations (B3LYP/LanL2DZ) of simplified models of [Mo(N(2))(2)(dppe)(2)] and the two protonated derivatives [MoF(NNH)(dppe)(2)] and [MoF(NNH(2))(dppe)(2)](+) (dppe = 1,2-bis(diphenylphosphino)ethane) provide quantitative insight into the reduction and protonation of dinitrogen bound end-on terminally to transition metals. This "asymmetric" reduction pathway is characterized by a stepwise increase of covalency and a concomitant charge donation from the metal center during each protonation reaction. The major part of metal-to-ligand charge transfer occurs after the first protonation leading to coordinated diazenido(-). In contrast, addition of the second proton is accompanied by a mino…
Ab initiocomputational study on the lattice thermal conductivity of Zintl clathrates[Si19P4]Cl4andNa4[Al4Si19]
2016
The lattice thermal conductivity of silicon clathrate framework ${\mathrm{Si}}_{23}$ and two Zintl clathrates, $[{\mathrm{Si}}_{19}{\mathrm{P}}_{4}]{\mathrm{Cl}}_{4}$ and ${\mathrm{Na}}_{4}[{\mathrm{Al}}_{4}{\mathrm{Si}}_{19}]$, is investigated by using an iterative solution of the linearized Boltzmann transport equation in conjunction with ab initio lattice dynamical techniques. At 300 K, the lattice thermal conductivities for ${\mathrm{Si}}_{23}, [{\mathrm{Si}}_{19}{\mathrm{P}}_{4}]{\mathrm{Cl}}_{4}$, and ${\mathrm{Na}}_{4}[{\mathrm{Al}}_{4}{\mathrm{Si}}_{19}]$ were found to be 43 W/(m K), 25 W/(m K), and 2 W/(m K), respectively. In the case of ${\mathrm{Na}}_{4}[{\mathrm{Al}}_{4}{\mathrm…
Glass Transition and Glass Dynamics
2014
The transition from an undercooled liquid towards a glass (glass transition) is introduced and discussed in terms of mode-coupling theory. It is demonstrated that mode-coupling theory leads to a two-step relaxation scenario near the transition with time-critical exponents, which characterize the two relaxation steps (beta and alpha relaxation). The anomalous vibrational properties of a disordered solid (glass) is explained in terms of a model with spatially fluctuating harmonic force constants.
A raman spectroscopic determination of the interlamellar forces in crystalline n-alkanes and of the limiting elastic modulus Ec of polyethylene
1976
A simple treatment based on continuum mechanics shows that weak interlamellar forces in crystalline n-alkanes should result in a characteristic upward shift of the frequencies of the longitudinal acoustical (LA) modes, which is independent of the chain length and decreases inversely with the mode order. A raman spectroscopic determination of the LA mode frequencies of a series of different n-alkanes confirms the theoretical conclusion and permits a derivation of a force constant characteristic of the interlamellar forces. The discussion results in a new formula valid for the LA mode frequencies of the orthorhombic n-alkanes in the acoustical limit and yields a new determination of the limit…