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Titolo:
HCP <-> CPH isomerization: Caught in the act
Autore:
Ishikawa, H; Field, RW; Farantos, SC; Joyeux, M; Koput, J; Beck, C; Schinke, R;
Indirizzi:
Tohoku Univ, Grad Sch Sci, Dept Chem, Sendai, Miyagi 9808578, Japan TohokuUniv Sendai Miyagi Japan 9808578 em, Sendai, Miyagi 9808578, Japan MIT, Dept Chem, Cambridge, MA 02139 USA MIT Cambridge MA USA 02139MIT, Dept Chem, Cambridge, MA 02139 USA Fdn Res & Technol Hellas, Inst Elect Struct & Laser, Hellas, Greece Fdn Res & Technol Hellas Hellas Greece t Struct & Laser, Hellas, Greece Univ Crete, Dept Chem, GR-71110 Iraklion, Crete, Greece Univ Crete Iraklion Crete Greece GR-71110 R-71110 Iraklion, Crete, Greece Univ Grenoble 1, Spectrometrie Phys Lab, F-38042 Grenoble, France Univ Grenoble 1 Grenoble France F-38042 ys Lab, F-38042 Grenoble, France Adam Mickiewicz Univ, Dept Chem, PL-60780 Poznan, Poland Adam Mickiewicz Univ Poznan Poland PL-60780 hem, PL-60780 Poznan, Poland Max Planck Inst Stromungsforsch, D-37073 Gottingen, Germany Max Planck Inst Stromungsforsch Gottingen Germany D-37073 ingen, Germany
Titolo Testata:
ANNUAL REVIEW OF PHYSICAL CHEMISTRY
, volume: 50, anno: 1999,
pagine: 443 - 484
SICI:
0066-426X(1999)50:<443:H<CICI>2.0.ZU;2-4
Fonte:
ISI
Lingua:
ENG
Soggetto:
EMISSION PUMPING SPECTROSCOPY; EXCITED VIBRATIONAL-STATES; DISPERSED FLUORESCENCE-SPECTRA; SEMI-CLASSICAL QUANTIZATION; PERIODIC ORBIT ANALYSIS; ENERGY-LEVELS; UNIMOLECULAR DISSOCIATION; FOURIER-TRANSFORM; INTRAMOLECULAR DYNAMICS; FILTER-DIAGONALIZATION;
Keywords:
vibrational spectroscopy; polyads; resonance Hamiltonian; bifurcations; periodic orbits;
Tipo documento:
Review
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
101
Recensione:
Indirizzi per estratti:
Indirizzo: Ishikawa, H Tohoku Univ, Grad Sch Sci, Dept Chem, Sendai, Miyagi 9808578, Japan Tohoku Univ Sendai Miyagi Japan 9808578 Miyagi 9808578, Japan
Citazione:
H. Ishikawa et al., "HCP <-> CPH isomerization: Caught in the act", ANN R PH CH, 50, 1999, pp. 443-484

Abstract

In this overview we discuss the vibrational spectrum of phosphaethyne, HCP, in its electronic ground state, as revealed by complementary experimentaland theoretical examinations. The main focus is the evolution of specific spectral patterns from the bottom of the potential well up to excitation energies of approximately 25,000 cm(-1), where large-amplitude, isomerization-type motion from H-CP to CP-H is prominent. Distinct structural and dynamical changes, caused by an abrupt transformation from essentially HC bondingto mainly PH bonding, set in around 13,000 cm(-1). They reflect saddle-node bifurcations in the classical phase space-a phenomenon well known in the nonlinear dynamics literature-and result in characteristic patterns in the spectrum and the quantum-number dependence of the vibrational fine-structure constants. Two polar opposites are employed to elucidate the spectral patterns: the exact solution of the Schrodinger equation, using an accurate potential energy surface and an effective or resonance Hamiltonian (expressedin a harmonic oscillator basis set and block diagonalized into polyads), which is defined by parameters adjusted to fit either the measured or the calculated vibrational energies. The combination of both approaches-together with classical mechanics and semiclassical analyses-provides a detailed spectroscopic picture of the breaking of one bond and the formation of a new one.

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Documento generato il 22/09/20 alle ore 20:47:53