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Titolo:
Approximate factorization of molecular potential surfaces II. Internal rotors
Autore:
Pearman, R; Gruebele, M;
Indirizzi:
Univ Illinois, Dept Chem, Urbana, IL 61801 USA Univ Illinois Urbana IL USA 61801 linois, Dept Chem, Urbana, IL 61801 USA Univ Illinois, Dept Biophys, Urbana, IL 61801 USA Univ Illinois Urbana ILUSA 61801 ois, Dept Biophys, Urbana, IL 61801 USA Univ Illinois, Beckman Inst Adv Sci & Technol, Urbana, IL 61801 USA Univ Illinois Urbana IL USA 61801 Adv Sci & Technol, Urbana, IL 61801 USA
Titolo Testata:
ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-INTERNATIONAL JOURNAL OF RESEARCH IN PHYSICAL CHEMISTRY & CHEMICAL PHYSICS
, volume: 214, anno: 2000,
parte:, 11
pagine: 1439 - 1466
SICI:
0942-9352(2000)214:<1439:AFOMPS>2.0.ZU;2-F
Fonte:
ISI
Lingua:
ENG
Soggetto:
INTRAMOLECULAR VIBRATIONAL REDISTRIBUTION; RANDOM-MATRIX TREATMENT; ENERGY-FLOW; EXCITED METHANOL; P-FLUOROTOLUENE; ROTATIONAL SPECTRUM; GROUND-STATE; DYNAMICS; RELAXATION; MODEL;
Keywords:
methanol; hydrogen peroxide; power-law;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
55
Recensione:
Indirizzi per estratti:
Indirizzo: Gruebele, M Univ Illinois, Dept Chem, Urbana, IL 61801 USA Univ Illinois Urbana IL USA 61801 Chem, Urbana, IL 61801 USA
Citazione:
R. Pearman e M. Gruebele, "Approximate factorization of molecular potential surfaces II. Internal rotors", Z PHYS CHEM, 214, 2000, pp. 1439-1466

Abstract

Scaling models for the polyatomic potential energy surface occupy a groundintermediate between ab initio surfaces and random matrix models. They areuseful for the study of vibrational energy redistribution (IVR) in large molecules, and have been shown to reproduce many features of more accurate spectroscopically fitted or ab initio potential surfaces. A previous analysis of potential constants and coupling matrix elements [J. Chem. Phys. 106 (1977) 5874] considered modes that maintain vibrational character up to the dissociation limit. Here we discuss factorization and scaling properties ofthe vibrational Hamiltonian in the presence of an internal rotor. We find that the "rotor effect" is most pronounced for delocalized skeletal vibrations, potentially resulting in increased NR of "bath" states compared to "bright" states. For localized vibrational modes that involve atomic displacements near the rotor, the local density of states is enhanced, while for more remote localized modes, the effect is negligible.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 11/07/20 alle ore 07:18:33