The OH stretching frequency in liquid water simulations: the classical error

摘要: Abstract OH stretching frequencies of HDO molecules in liquid water have been calculated by molecular dynamics simulation and compared to quantum-corrected frequencies. In the MD MCY intermolecular water—water potential was used together with an experimental intramolecular free potential. The classically Fourier transformation velocity autocorrelation function are found be ≈300 cm −1 too high experiment. Quantum corrections show that classical error contribution this discrepancy is ≈140 . To reach full agreement experiment, also model needs improved. It suggested constructing flexible potentials goal should not set for MD-derived frequency absolute experiment (at 3400 ) but instead some 200 higher.