Efficient quantum calculations of vibrational states of vinylidene in full dimensionality: a scheme with combination of methods.
Full-dimensional quantum calculations of vibrational states of C(2)H(2) and C(2)D(2) are performed in the high-energy region (above 20,400 cm(-1) relative to the acetylene minimum). The theoretical scheme is a combination of several methods. To exploit the full parity and permutation symmetry, the CC-HH diatom-diatom Jacobi coordinates are chosen; phase space optimization in combination with physical considerations is used to obtain an efficient radial discrete variable representation, whereas a basis contraction scheme is applied for angular coordinates. The preconditioned inexact spectral transform method combined with an efficient preconditioner is employed to compute eigenstates within a desired spectral window. The computation is efficient. More definite assignments on vinylidene states than previous studies are acquired using the normal mode projection; in particular, a consistent analysis of the nu(1) (symmetric CH stretch) state is provided. The computed vinylidene vibrational energy levels are in general good agreement with experiment, and several vinylidene states are reported for the first time.
Li
Bin
B
Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, People's Republic of China.
Bian
Wensheng
W