Absolute intensities of NH-stretching transitions in dimethylamine and pyrrole

TY - JOUR

T1 - Absolute intensities of NH-stretching transitions in dimethylamine and pyrrole

AU - Miller, Benjamin J.

AU - Du, Lin

AU - Steel, Thomas J.

AU - Paul, Allanah J.

AU - Sodergren, A. Helena

AU - Lane, Joseph R.

AU - Henry, Bryan R.

AU - Kjærgaard, Henrik Grum

PY - 2012/1/12

Y1 - 2012/1/12

N2 - Vibrational spectra of vapor-phase dimethylamine (DMA) and pyrrole have been recorded in the 1000 to 13000 cm -1 region using long path conventional spectroscopy techniques. We have focused on the absolute intensities of the NH-stretching fundamental and overtone transitions; δν NH = 1-4 regions for DMA and the δν NH = 1-3 regions for pyrrole. In the δν NH = 1-3 regions for DMA, evidence of tunneling splitting associated with the NH-wagging mode is observed. For DMA, the fundamental NH-stretching transition intensity is weaker than the first NH-stretching overtone. Also, the fundamental NH-stretching transition in DMA is much weaker than the fundamental transition in pyrrole. We have used an anharmonic oscillator local mode model with ab initio calculated local mode parameters and dipole moment functions at the CCSD(T)/aug-cc-pVTZ level to calculate the NH-stretching intensities and explain this intensity anomaly in DMA.

AB - Vibrational spectra of vapor-phase dimethylamine (DMA) and pyrrole have been recorded in the 1000 to 13000 cm -1 region using long path conventional spectroscopy techniques. We have focused on the absolute intensities of the NH-stretching fundamental and overtone transitions; δν NH = 1-4 regions for DMA and the δν NH = 1-3 regions for pyrrole. In the δν NH = 1-3 regions for DMA, evidence of tunneling splitting associated with the NH-wagging mode is observed. For DMA, the fundamental NH-stretching transition intensity is weaker than the first NH-stretching overtone. Also, the fundamental NH-stretching transition in DMA is much weaker than the fundamental transition in pyrrole. We have used an anharmonic oscillator local mode model with ab initio calculated local mode parameters and dipole moment functions at the CCSD(T)/aug-cc-pVTZ level to calculate the NH-stretching intensities and explain this intensity anomaly in DMA.

U2 - 10.1021/jp209118p

DO - 10.1021/jp209118p

M3 - Journal article

C2 - 22074457

SN - 1089-5639

VL - 116

SP - 290

EP - 296

JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

IS - 1

ER -