TY - JOUR
T1 - Phase space optimization of quantum representations
T2 - Non-Cartesian coordinate spaces
AU - Poirier, Bill
N1 - Funding Information:
I would like to thank Professor John C. Light for his support and guidance, and for many useful discussions. This work was supported, in part, by the Department of Energy under Grant DE-FG02-87 ER1367 9, and by the American Chemical Society Petroleum Research Fund, under Grant PRF #37209-G6.
PY - 2001/11
Y1 - 2001/11
N2 - In an earlier article [Found. Phys. 30, 1191 (2000)], a quasiclassical phase space approximation for quantum projection operators was presented, whose accuracy increases in the limit of large basis size (projection subspace dimensionality). In a second paper [J. Chem. Phys. 111, 4869 (1999)], this approximation was used to generate a nearly optimal direct-product basis for representing an arbitrary (Cartesian) quantum Hamiltonian, within a given energy range of interest. From a few reduced-dimensional integrals, the method determines the optimal 1D marginal Hamiltonians, whose eigenstates comprise the direct-product basis. In the present paper, this phase space optimized direct-product basis method is generalized to incorporate non-Cartesian coordinate spaces, composed of radii and angles, that arise in molecular applications. Analytical results are presented for certain standard systems, including rigid rotors, and three-body vibrators.
AB - In an earlier article [Found. Phys. 30, 1191 (2000)], a quasiclassical phase space approximation for quantum projection operators was presented, whose accuracy increases in the limit of large basis size (projection subspace dimensionality). In a second paper [J. Chem. Phys. 111, 4869 (1999)], this approximation was used to generate a nearly optimal direct-product basis for representing an arbitrary (Cartesian) quantum Hamiltonian, within a given energy range of interest. From a few reduced-dimensional integrals, the method determines the optimal 1D marginal Hamiltonians, whose eigenstates comprise the direct-product basis. In the present paper, this phase space optimized direct-product basis method is generalized to incorporate non-Cartesian coordinate spaces, composed of radii and angles, that arise in molecular applications. Analytical results are presented for certain standard systems, including rigid rotors, and three-body vibrators.
UR - http://www.scopus.com/inward/record.url?scp=0035732893&partnerID=8YFLogxK
U2 - 10.1023/A:1012642832253
DO - 10.1023/A:1012642832253
M3 - Article
AN - SCOPUS:0035732893
SN - 0015-9018
VL - 31
SP - 1581
EP - 1610
JO - Foundations of Physics
JF - Foundations of Physics
IS - 11
ER -