High resolution (0.004cm(-1) instrumental bandwidth) interferometric Fourier transform infrared spectra of (ND3)-N-14 were obtained on a BOMEM DA002 spectrometer under essentially Doppler limited conditions. An analysis is reported of the ND3 stretching fundamentals with band centres at <(nu)over tilde>(0)(1) (s <-- a) = (2420.056 +/- 0.00 cm(-1), <(nu)over tilde>(0)(3) (a <-- s) = (2420.650 +/- 0.001) cm(-1) <(nu)over tilde>(0)(3)(a <-- a) = (2563.8840 +/- 0.0005)cm(-1) and <(nu)over tilde>(0)(3) (S <-- S) = (2563.9161 +/- 0.0005) cm(-1) with inversion tunnelling splittings Delta<(nu)over tilde>(1) = 0.5412cm(-1) and Delta<(nu)over tilde>(3) = 0.0209cm(-1) in the vibrationally excited levels. About 50 parameters of the effective Hamiltonian for this band system could be determined accurately. Assignments were established with certainty by means of ground state combination differences. The results are important for and are discussed in relation to the mode selective inhibition and promotion of inversion at the nitrogen atom by exciting ND stretching vibrations, and treatments of isotope effects on inversion df ammonia by means of effective Hamiltonians and true molecular Hamiltonians on high dimensional potential hypersurfaces.
The nu(1) and nu(3) bands of ND3
Snels M;
2000
Abstract
High resolution (0.004cm(-1) instrumental bandwidth) interferometric Fourier transform infrared spectra of (ND3)-N-14 were obtained on a BOMEM DA002 spectrometer under essentially Doppler limited conditions. An analysis is reported of the ND3 stretching fundamentals with band centres at <(nu)over tilde>(0)(1) (s <-- a) = (2420.056 +/- 0.00 cm(-1), <(nu)over tilde>(0)(3) (a <-- s) = (2420.650 +/- 0.001) cm(-1) <(nu)over tilde>(0)(3)(a <-- a) = (2563.8840 +/- 0.0005)cm(-1) and <(nu)over tilde>(0)(3) (S <-- S) = (2563.9161 +/- 0.0005) cm(-1) with inversion tunnelling splittings Delta<(nu)over tilde>(1) = 0.5412cm(-1) and Delta<(nu)over tilde>(3) = 0.0209cm(-1) in the vibrationally excited levels. About 50 parameters of the effective Hamiltonian for this band system could be determined accurately. Assignments were established with certainty by means of ground state combination differences. The results are important for and are discussed in relation to the mode selective inhibition and promotion of inversion at the nitrogen atom by exciting ND stretching vibrations, and treatments of isotope effects on inversion df ammonia by means of effective Hamiltonians and true molecular Hamiltonians on high dimensional potential hypersurfaces.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.


