TY - JOUR
T1 - Vibrational motion in isotopomers of the HeH+ molecular ion
T2 - An application of the electron nuclear dynamics method
AU - Bergson, Göran
AU - Calais, Jean Louis
AU - Morales, Jorge
AU - Öhrn, Yngve
PY - 1997
Y1 - 1997
N2 - The importance of isotopic substitution as a tool for elucidation of chemical reaction events originates in the fact mat the Coulombic Hamiltonian is isotopically invariant except for the nuclear kinetic energy term. Thus, in theories of isotope effects based on the Born - Oppenheimer scheme, the basic presumption is the invariance of the potential energy surface (PES). We use, however, a fully dynamic approach, called Electron Nuclear Dynamics (END), which does net require a preconstructed PES. Since the END formalism is rather different from commonly used procedures, we study the anharmonic nuclear vibration in isotopic species of the HeH+ molecular ion as a model problem. A single time-dependent complex parametrized determinantal wave function is used for the electrons and the nuclei are treated classically. The time evolution of the nuclear and electronic dynamical variables obtained by integration of equations of motion are reported as bond length, nuclear kinetic energy, and Mulliken populations. The molecule vibrates as a classical object. The product of the reduced mass and the square of the vibrational frequency is isotopomer invariant for any common total energy. The difference between the total energy and the nuclear kinetic energy as a function of the intemudear distance is interpreted as the average dynamic potential.
AB - The importance of isotopic substitution as a tool for elucidation of chemical reaction events originates in the fact mat the Coulombic Hamiltonian is isotopically invariant except for the nuclear kinetic energy term. Thus, in theories of isotope effects based on the Born - Oppenheimer scheme, the basic presumption is the invariance of the potential energy surface (PES). We use, however, a fully dynamic approach, called Electron Nuclear Dynamics (END), which does net require a preconstructed PES. Since the END formalism is rather different from commonly used procedures, we study the anharmonic nuclear vibration in isotopic species of the HeH+ molecular ion as a model problem. A single time-dependent complex parametrized determinantal wave function is used for the electrons and the nuclei are treated classically. The time evolution of the nuclear and electronic dynamical variables obtained by integration of equations of motion are reported as bond length, nuclear kinetic energy, and Mulliken populations. The molecule vibrates as a classical object. The product of the reduced mass and the square of the vibrational frequency is isotopomer invariant for any common total energy. The difference between the total energy and the nuclear kinetic energy as a function of the intemudear distance is interpreted as the average dynamic potential.
UR - http://www.scopus.com/inward/record.url?scp=4344563129&partnerID=8YFLogxK
U2 - 10.1002/(SICI)1097-461X(1997)63:2<415::AID-QUA12>3.0.CO;2-7
DO - 10.1002/(SICI)1097-461X(1997)63:2<415::AID-QUA12>3.0.CO;2-7
M3 - Article
AN - SCOPUS:4344563129
SN - 0020-7608
VL - 63
SP - 415
EP - 424
JO - International Journal of Quantum Chemistry
JF - International Journal of Quantum Chemistry
IS - 2
ER -