Adiabatic Switching Extended to Prepare Semiclassically Quantized Rotational-Vibrational Initial States for Quasiclassical Trajectory Calculations
  • Metaadatok
Tartalom: http://real.mtak.hu/62360/
Archívum: MTA Könyvtár
Gyűjtemény: Status = Published

Type = Article
Cím:
Adiabatic Switching Extended to Prepare Semiclassically Quantized Rotational-Vibrational Initial States for Quasiclassical Trajectory Calculations
Létrehozó:
Nagy, Tibor
Lendvay, György
Kiadó:
American Chemical Society
Dátum:
2017
Téma:
QD02 Physical chemistry / fizikai kémia
Tartalmi leírás:
An approximation-free adiabatic switching method to generate
semiclassically quantized ensembles of rovibrational states of
polyatomic molecules for use as initial conditions in
quasiclassical trajectory calculations is presented.
Vibrational states are prepared starting from an ensemble of
classical states corresponding to the desired quantum state of
the normal mode Hamiltonian by slowly switching on the
anharmonicity in internal coordinates thereby avoiding
rotational contamination. To generate rovibrational states, an
extension is proposed: the vibrationally quantized molecules
are slowly spun up to the desired quantized angular momentum.
The ensembles obtained with adiabatic switching for CH4 are
insensitive to the choice of internal coordinates and
stationary, furthermore, their mean energies agree remarkably
well with the quantum mechanical values: the zero-point energy
and 15 vibrational levels of the first three polyads within 20
cm-1, the rotational levels between J=1-50 within 1%; the
standard deviation is always less than 1%. Adiabatic switching
produces classical state ensembles with significantly better
properties than normal mode sampling, making them more
appropriate in QCT calculations.
Nyelv:
angol
angol
Típus:
Article
PeerReviewed
info:eu-repo/semantics/article
Formátum:
text
text
Azonosító:
Nagy, Tibor and Lendvay, György (2017) Adiabatic Switching Extended to Prepare Semiclassically Quantized Rotational-Vibrational Initial States for Quasiclassical Trajectory Calculations. JOURNAL OF PHYSICAL CHEMISTRY LETTERS. pp. 1-19. ISSN 1948-7185
Kapcsolat:
https://doi.org/10.1021/acs.jpclett.7b01838
MTMT:3265377; doi:10.1021/acs.jpclett.7b01838