Highly Excited Vibrational States of the KCN Molecule
نویسنده
چکیده
Vibrational (J = 0) states for the KCN molecule are calculated in Jacobi coordinates, employing a discrete variable representation (DVR) for the angular internal coordinate. The power of the DVR method is once again illustrated in that some 800 vibrational (J = 0) states are converged for a two-dimensional potential-energy surface. The energy region studied is that where the classical dynamics of the system are known to be chaotic. Most of the states are found to be irregular, although there are classes which appear to be regular and can be assigned effective quantum numbers corresponding to excitation in particular 'separable' modes of the system. Phenomenological aspects of the wavefunctions are discovered via graphical analysis, in particular many linearly localised states are identified where the potential-energy surface actually has a saddle point. The statistical behaviour of the level spacings is also investigated. Comparison with a similar study on LiCN (J. R. Henderson and J. Tennyson, Mol. Phys., 1990,69,639) is made.
منابع مشابه
Highly excited vibrational states of HCN around 30 000 cm-1.
This article describes the analysis and interpretation of rovibrational spectra involving highly excited vibrational states in the molecule of HCN. The spectra were obtained by means of the vibrationally mediated photodissociation technique. Analysis of the spectra revealed four bands with Sigma-Sigma structures that, once fitted, provided the energies and rotational constants of four new, high...
متن کاملHighly excited vibrational eigenstates of nonlinear triatomic molecules. Application to H2O
Highly accurate quantum-mechanical calculations az presented for highly excited vibrational states of HzO. The vibration Hamiltonian operator Hvib for a nonlinear triatomic molecule is given in Radau coordinates. A direct product basis is chosen, and the Hvib matrix is evaluated in the discrete variable representation (DVR) for the symmetrized Radau coordinates. Vibrational eigenstates are comp...
متن کاملOptimization of vibrational coordinates
The enormous progress made in recent years in the techniques for detecting and analysing highly excited vibrational states of polyatomic molecules has prompted development of theoretical quantum mechanical methods to determine and characterize these states. A number of techniques, both approximate and exact, have been proposed for solving the vibrational Schro dinger equation and special atten...
متن کاملThe highly excited C - H stretching states of CHD 3 , CHT 3 , and CH 3 D
Unlike many other molecules having local modes, the highly excited C-H stretching states of CHD3 show well resolved experimental spectra and simple Fermi resonance behavior. In this paper the local mode features in this prototype molecule are examined using a curvilinear coordinate approach. Theory and experiment are used to identify the vibrational state coupling. Both kinetic and potential te...
متن کاملFluorescence Spectrophotometry
Fluorescence and phosphorescence are photon emission processes that occur during molecular relaxation from electronic excited states. These photonic processes involve transitions between electronic and vibrational states of polyatomic fluorescent molecules (fluorophores). The Jablonski diagram (Figure 1) offers a convenient representation of the excited state structure and the relevant transiti...
متن کامل